Polymerization process

ABSTRACT

This invention relates to a process to polymerize olefins comprising contacting a catalyst or catalyst system with olefin(s) in the presence of a fluorocarbon at a temperature above the onset melting point of the polymer. 
     This invention also relates to a solution process to polymerize olefins comprising contacting a catalyst or catalyst system with olefin(s) in the presence of a fluorocarbon at a temperature above the onset melting point of the polymer.

PRIORITY CLAIM

This application is the national phase entry into the United StatesPatent Office of international application number PCT/US2005/021731filed Jun. 20, 2005, which claims benefit of and priority to U.S.Provisional Patent Application Ser. No. 60/581,425 filed Jun. 21, 2004.

FIELD OF THE INVENTION

This invention relates to the use of a fluorocarbon in an olefinpolymerization process operating at a temperature above the onsetmelting point of the polymer being produced.

BACKGROUND OF THE INVENTION

Unsaturated monomers, particular olefin monomers, are polymerized in avariety of polymerization processes using a wide variety of catalystsand catalyst systems. One of the most common polymerization process usedin the production of olefin based polymers such as polyethylene,polypropylene, polybutene, etc, is a solution based process. In such aprocess the formed polymer is dissolved in the polymerization medium.Often, the catalyst and monomer are also dissolved in the polymerizationmedium, but that is not a requirement of a “solution” process. Intypical solution processes, the polymerization temperature may be at,above or below the melting point of the dry polymer. For example, intypical solution phase polyethylene processes, polymerization takesplace in a hydrocarbon solvent at temperatures above the melting pointof the polymer and the polymer is typically recovered by vaporization ofthe solvent and any unreacted monomer. In some cases solvents are usedas the polymerization medium while in others, the monomer to bepolymerized also acts as the solvent (e.g. a bulk process).

In each of these systems, there remain factors that influence not onlythe rate and volume at which the polymerization can run, but can alsoinfluence the properties of polymer produced. In a solution process, thepolymer formed is dissolved in the polymerization medium. The higher theconcentration of the polymer, the higher the viscosity of thepolymerization reaction mixture containing polymer, monomers andsolvent. High viscosity in the polymerization reactor associated withsolution process is a limiting step for process efficiency and polymerproduction. High viscosity can also lead to the difficulty for efficientmixing in the reactor to maintain a homogeneous system and avoid productproperty drift (heterogeneity), reactor safety, process controlproblems. This is especially true for processes of polymerization withpolymers having molecular weights higher than the entanglement molecularweights. Higher operating temperature reduces the viscosity, however themolecular weight of the polymer tends to decrease with reactiontemperature. Thus production of higher molecular weight polymers insolution processes is generally limited by the viscosity of thepolymerization medium. This problem exists even with the advent of newcatalyst systems. In some situations, metallocene catalysts allowpolymerizations to be performed at a high temperatures, such that ahigher polymer concentration in the reactor effluent is obtained (ascompared to that of a conventional solution process) with reducedoperation difficulties.

Polymer solutions can undergo phase separation at the lower criticalsolution temperature. The phase separation is encouraged by highertemperature and/or lower pressure. Appropriate selection ofpolymerization solvent, monomer conversion, especially of the volatilemonomers, temperatures, and pressures is required to avoid phaseseparation. Solvents such as hexane may require an elevated operatingpressure of above 50 bar (5000 kPa) to avoid unwanted phase separation.In solution plants, solvent selection and operating conditions must bedesigned for a particular operating windows for the desiredpolymerization process. This operating window might not be permitted byor optimized for a given polymer type and catalyst.

Polymers with low crystallinity or amorphous character as well as thosewith higher crystallinities are currently produced in slurry and orsuspension processes using hydrocarbon solvents as diluents. Thesuspension process can advantageously handle polymer concentrations inthe reactor effluent up to 25-30 wt %, as compared to 7-18 wt % in thesolution process which are limited by solution viscosity at a high levelof solids content. These higher concentrations are attributable to thecharacteristics of decreasing polymer-polymer entanglements in thesuspension process by forcing the entangled polymer into the dispersedand or suspended phase thereby decreasing the concentration of entangledpolymer in the bulk reactor solution phase. The recovery of polymer isalso simpler in the slurry process. However, it is necessary that thesolid particles in the slurry process do not agglomerate to one anotheror adhere to the surfaces of the reactor wall and the transport lines.Extremely low operating temperatures are adopted to reduce the solublefraction of polymer in the solvent. Mitigation of polymer fouling is achallenging task.

Many polymers are insoluble in the reaction mixture from which they areformed. Upon significant polymerization, polymer chains reach acrystallizable length and polymer nucleation and crystallization begin.The crystallization of polymers leads to polymer-solvent phaseseparation. On the other hand, polymer-solvent phase separation can bealso induced through change of solvency of the reaction medium withrespect to the polymer produced. The instant invention provides aprocess that with proper selection of a fluorinated hydrocarbon or amixture of fluorinated hydrocarbons and hydrocarbon solvents, can beoperated in a suspension mode instead of solution. There is a need forpolymerization processes which efficiently produce polymer, particularlyof higher molecular weight, with reduced operation difficulties and/orreduced reactor fouling.

U.S. Pat. No. 3,470,143 discloses a process to produce a boiling-xylenesoluble polymer in a slurry using certain fluorinated organic carboncompounds.

U.S. Pat. No. 5,990,251 discloses a gas phase process using aZiegler-Natta catalyst system modified with a halogenated hydrocarbon,such as chloroform.

EP 0 459 320 A2 discloses polymerization in polar aprotic solvents, suchas halogenated hydrocarbons.

U.S. Pat. No. 5,780,565 discloses dispersion polymerizations of polarmonomers under super-atmospheric conditions such that the fluid is aliquid or supercritical fluid, the fluid being carbon dioxide, ahydrofluorocarbon, a perfluorocarbon or a mixture thereof.

U.S. Pat. No. 5,624,878 discloses the polymerization using “constrainedgeometry metal complexes” of titanium and zirconium.

U.S. Pat. Nos. 2,534,698, 2,644,809 and 2,548,415 disclose preparationof butyl rubber type elastomers in fluorinated solvents.

U.S. Pat. No. 6,534,613 discloses use of hydrofluorocarbons as catalystmodifiers.

U.S. Pat. No. 4,950,724 disclose the polymerization of vinyl aromaticmonomers in suspension polymerization using fluorinated aliphaticorganic compounds.

WO 02/34794 discloses free radical polymerizations in certainhydrofluorocarbons.

WO 02/04120 discloses a fluorous bi-phasic systems.

WO 02/059161 discloses polymerization of isobutylene using fluorinatedco-initiators.

EP 1 323 746 discloses a method of supporting a catalyst using solubleand insoluble liquids, such as hydrocarbon/halocarbon mixtures. Example1 of EP 1 323 746 shows loading of biscyclopentadienyl catalyst onto asilica support in perfluorooctane and thereafter the prepolymerizationof ethylene at room temperature.

U.S. Pat. No. 3,056,771 discloses polymerization of ethylene usingTiCl₄/(Et₃Al in a mixture of heptane and perfluoromethylcyclohexane,presumably at room temperature. Additional references of interestinclude: Designing Solvent Solutions, Chemical and Engineering News,Oct. 13, 2003 (www.CEN-online.org); Polymer Synthesis UsingHydrofluorocarbon Solvents., Wood, Colin, et al. Macromolecules, Vol.35, Number 18, pages 6743-6746, 2002; Perfluorinated Polyethers for theImmobilisation of Homogeneous Nickel Catalysts, Keim, W. et al., Journalof Molecular Catalysis A: Chemical 139 (1999) 171-175; RU2195465;US20020086908 A1; WO200251875 A1; US2002/0032291 A1; U.S. Pat. Nos.3,397,166; 3,440,219; 6,111,062;5,789,504; 5,703,194; 5,663,251;5,608,002; 5,494,984; 5,310,870; 5,182,342; 2,603,626; 2,494,585;2,474,571; WO 02/051875 A1; U.S. Pat. Nos. 6,133,389; 6,096,840;6,107,423; 6,037,483; 5,981,673; 5,939,502; 5,939,501; 5,674,957;5,872,198; 5,959,050; 5,821,311; 5,807,977; 5,688,838; 5,668,251;5,668,250; 5,665,838; 5,663,255; 5,552,500; 5,478,905;5,459,212;5,281,680; 5,135,998; 5,105,047; 5,032,656;4,166,165; 4,123,602;4,100,225; 4,042,634; US 2002/0132910 A1; US 2002/0151664 A1; US2002/0183457 A1; US 2002/0183471 A1; US 2003/0023013 A1; US 2001/0012880A1; US 2001/0018144 A1; US 2002/0002219 A1; US 2002/0028884 A1; US2002/0052454 A1; US 2002/0055580 A1; US 2002/0055581; US 2002/0055599A1, US 2002/0065383; US 2002/0086908 A1; US 2002/0128411 A1; U.S. Pat.Nos. 3,269,972, 3,331,822;3,493,530; 3,528,954; 3,590,025; 3,616,371;3,642,742;3,787,379; 3,919,183; 3,996,281; 4,194,073; 4,338,237;4,381,387; 4,424,324; 4,435,553; 4,452,960; 4,499,249;4,508,881;4,535,136; 4,588,796; 4,626,608; 4,736,004;4,900,777; 4,946,936;4,948,844; WO00/50209; WO/96/24625; WO 94/17109; WO 0149760 A1; WO01/49758 A1; WO 01/49757; WO 00/53682; WO 00/47641; U.S. Pat. Nos.6,486,280 B1; 6,469,185 B1 ; 6,469,116 B2;6,455,650 B1; 6,448,368 B1;6,423,798 B2; EP 0 076 511 B1; EP 0 271 243 B1; U.S. Pat. Nos. 6,417,314B1; 6,399,729 B1; 6,380,351 B1; 6,372,838 B1; 6,346,587 B1; 6,337,373B1; 6,335,408 B1; 6,306,989 B1; 6,228,963 B1; 6,225,367 B1; JP 7033821 Bpublished Apr. 12, 1995; JP 11349606 A published Dec. 21, 1999; and JP61007307 published Jan. 14, 1986.

SUMMARY OF THE INVENTION

This invention relates to a process to produce polyolefins comprisingcontacting a catalyst or catalyst system with olefin(s) in the presenceof a fluorinated hydrocarbon at a polymerization temperature above theonset melting point of the wet polymer, provided that if the polymerdoes not have an onset melting point, then the polymerizationtemperature is 70° C. or more, wherein the fluorinated hydrocarbon ispresent at 5 to 99 volume %, based upon the total volume offluorocarbons, any hydrocarbon solvents present and any unreactedmonomer.

This invention relates to a process to polymerize olefins comprisingcontacting a catalyst or catalyst system with olefin(s) in the presenceof a fluorocarbon at a temperature above the onset melting point of thepolymer provided that if the dry polymer has no measurable meltingpoint, then the temperature is 70° C. or more.

In another embodiment, this invention relates to a process to polymerizeolefins comprising contacting a catalyst or catalyst system witholefin(s) in the presence of a fluorocarbon at a temperature above 70°C.

DEFINITIONS

For purposes of this invention and the claims thereto, the termcopolymers means any polymer comprising two or more monomers.

For the purposes of this invention and the claims thereto when a polymeris referred to as comprising a monomer, the monomer present in thepolymer is the polymerized form of the monomer. Likewise when catalystcomponents are described as comprising neutral stable forms of thecomponents, it is well understood by one of ordinary skill in the art,that the active form of the component is the form that reacts with themonomers to produce polymers. In addition, a reactor is any container(s)in which a chemical reaction occurs.

As used herein, the new notation numbering scheme for the Periodic TableGroups are used as set out in CHEMICAL AND ENGINEERING NEWS, 63(5), 27(1985).

As used herein, Me is methyl, t-Bu and ^(t)Bu are tertiary butyl, iPrand ^(i)Pr are isopropyl, Cy is cyclohexyl, and Ph is phenyl.

For purposes of this disclosure, the term oligomer refers tocompositions having 2-75 mer units and the term polymer refers tocompositions having 76 or more mer units. A mer is defined as a unit ofan oligomer or polymer that originally corresponded to the monomer(s)used in the oligomerization or polymerization reaction. For example, themer of polyethylene would be ethylene.

The term “catalyst system” is defined to mean a catalystprecursor/activator pair. When “catalyst system” is used to describesuch a pair before activation, it means the unactivated catalyst(precatalyst) together with an activator and, optionally, aco-activator. When it is used to describe such a pair after activation,it means the activated catalyst and the activator or othercharge-balancing moiety.

The transition metal compound may be neutral as in a precatalyst, or acharged species with a counter ion as in an activated catalyst system.

Catalyst precursor is also often referred to as precatalyst, catalyst,catalyst compound, catalyst precursor, transition metal compound ortransition metal complex. These words are used interchangeably.Activator and cocatalyst are also used interchangeably.

An amorphous polymer is defined as a polymer having a crystallinity of3% or less, as measured by DSC described below. A semi-crystallinepolymer is defined as a polymer having a crystallinity of 4% or more,preferably 5% or more, preferably 10% or more, preferably 15% or more,preferably 20% or more, preferably 30% or more, preferably 40% or more,preferably 50% or more, preferably 60% or more, preferably 70% or more.

DETAILED DESCRIPTION

In a preferred embodiment, this invention relates to a process topolymerize olefins comprising contacting a catalyst or catalyst systemwith olefin(s) in the presence of a fluorocarbon at a temperature abovethe onset melting point of the wet polymer, preferably at a temperatureabove the melting point of the wet polymer, preferably above the finalmelting point of the wet polymer, preferably at a temperature at least10° C. above the melting point of the wet polymer, preferably at atemperature at least 15° C. above the melting point of the wet polymer,preferably at a temperature at least 20° C. above the melting point ofthe wet polymer, preferably at a temperature at least 25° C. above themelting point of the wet polymer, preferably at a temperature at least30° C. above the melting point of the wet polymer, preferably at atemperature at least 35° C. above the melting point of the wet polymer,preferably at a temperature at least 40° C. above the melting point ofthe wet polymer, preferably at a temperature at least 50° C. above themelting point of the wet polymer, preferably at a temperature at least60° C. above the melting point of the wet polymer, preferably at atemperature at least 70° C. above the melting point of the wet polymer,preferably at a temperature at least 80° C. above the melting point ofthe wet polymer, preferably at a temperature at least 90° C. above themelting point of the wet polymer, preferably at a temperature at least100° C. above the melting point of the wet polymer, preferably at atemperature at least 110° C. above the melting point of the wet polymer,preferably at a temperature at least 120° C. above the melting point ofthe wet polymer, preferably at a temperature at least 150° C. above themelting point of the wet polymer.

By wet polymer is meant that prior to measurement the polymer inquestion has been contacted with the fluorocarbon(s) and or hydrocarbonsolvent/diluent(s) used in the polymerization process for at lest 12hours at 50° C. in a sealed chamber. The fluorocarbons and hydrocarbonsused to treat the polymer sample are to be the same fluorocarbons andhydrocarbons used in the polymerization medium present in the sameproportions.

By onset melting point of the wet polymer (Tm^(i)) is meant the onsetpoint in the melting curve of a differential scanning calorimetry (DSC)trace of the wet polymer.

By melting point of the wet polymer (Tm) is meant the peak temperatureon the melting curve of a differential scanning calorimetry (DSC) traceof the wet polymer

By final melting point of the wet polymer (Tm^(F)) is meant the endingpoint on the melting curve of a differential scanning calorimetry (DSC)trace of the wet polymer.

The differential scanning calorimetric (DSC) trace data is obtainedusing a TA Instruments model 2910 machine. Samples weighingapproximately 7-10 mg are sealed in aluminum sample pans or for wetpolymers the 7 to 10 mg sample is charged into a hermetically sealedcapsule (available from Perkin Elmer as part number B0182901 capsulekit). The DSC data are recorded by first cooling the sample to −100° C.and then gradually heating it to 200° C. at a rate of 10° C./minute. Thesample is kept at 200° C. for 5 minutes before a second cooling-heatingcycle is applied. Both the first and second cycle thermal events arerecorded.

While not wishing to be bound by theory, it is believed that addition offluorocarbon into the reaction medium reduces the solvency of thereaction medium with respect to the polymer produced and leads topolymer-solvent phase separation and that amorphous polymer stays insuspension state after phase separation.

Likewise, while not wishing to be bound by theory, it is believed thatfluorinated hydrocarbons (FC's) that are selected so that they aremiscible with hydrocarbon (HC's) solvents allow olefin monomers todissolve in that HC—FC solution but that the product polymer remainsinsoluble in that HC—FC medium. The extent of fluorination of a givencarbon number hydrocarbon is chosen such that it is miscible with thehydrocarbon solvent and monomer medium but is capable of modifying theresulting hydrocarbon fluorocarbon reaction medium such that themajority or all of the produced polymer phase separates into a polymerrich phase. Agitation results in this polymer rich phase being dispersedin small droplets throughout the hydrocarbon/fluorocarbon reactor liquidphase. Thus it is believed that at start up polymerization commences ina homogeneous solution phase but the first polymer phase separatesforming many small droplets which swirl around as a suspension in theHC—FC medium. In this way the reactor liquid viscosity remainsrelatively low since all the polymer chains creating entanglements andincreased viscosity are now in multitudes of little droplets of polymerconcentrate. These polymer droplets are believed to contain entanglementand a limited amount of HC solvent as well as some olefinic monomers buttheir influence on the bulk reactor viscosity has been removed. Nowdepending upon how the catalyst is designed one could arrange to have acatalyst largely soluble in the HC—FC medium or largely soluble in thepolymer droplets or alternatively partitioned between the HC—FC andpolymer droplet phases. Olefinic monomers will typically partitionbetween these two phases. In the HC—FC phase, olefins will polymerizegiving a polymer chain which immediately phase separates and coalesceswith existing polymer droplets or forms a new droplet. In the polymerdroplets olefins will polymerize to give a polymer chain in-situ in thedroplet. In cases where the already formed polymer chains have vinylchain ends (ethylene polymers and propylene polymers made at highertemperatures where beta methyl elimination is favored) the catalyst (e.ga metallocene) may allow polymer chain end copolymerization thusproducing polymers with significant long chain branching. Finally, asthe two (or more) phase effluent passes the first flash devolatilizingvessel, HC solvent, unreacted monomers and FC's are removed as vapourand the polymer droplets coalesce to a single polymer rich liquid phase.In a preferred embodiment the polymerization medium further comprises ahydrocarbon and the fluorocarbon is miscible with the hydrocarbon,preferably the fluorocarbon is miscible with the hydrocarbondiluent/monomer solution but causes phase separation of any polymerformed at reaction polymerization conditions.

In a preferred embodiment, one or more fluorocarbons are added to apolymerization process operating at a temperature above the onsetmelting point of the wet polymer in a polymerization reactor in anamount effective to induce precipitation of polymers produced or phaseseparation between the polymer produced and the liquid medium. Theprecipitated polymers remain in solid state or molten state during thepolymerization in the reaction medium under polymerization reactioncondition. Preferably at least 5% of polymers in the reaction medium isin solid or molten state in droplet or particle forms. Preferably uponaddition of a fluorocarbon at least 0.1 weight % of the reaction mediumis polymer present as solid particles, preferably at least 5 weight % ofthe reaction medium is present as solid particles, more preferablybetween 5 and 50 weight % is present as solid particles, more preferablybetween 10 and 45 weight %, more preferably between 15 and 40 weight %,more preferably between 20 and 35 weight %, more preferably between 25and 30 weight % is present as solid particles.

In a preferred embodiment, the polymerization process is one where themonomer(s) to be polymerized are used as the reaction medium (regardlessof whether the monomers act as solvent or diluent) and one or morefluorocarbons are added to the polymerization reactor in an amounteffective to induce precipitation of polymers produced. The precipitatedpolymers remain in solid state in droplet or particle forms during thepolymerization. Preferably upon addition of a fluorocarbon at least 0.1weight % of the reaction medium is polymer present as solid particles,preferably at least 5 weight % of the reaction medium is present assolid particles, more preferably between 5 and 50 weight % is present assolid particles, more preferably between 10 and 45 weight %, morepreferably between 15 and 40 weight %, more preferably between 20 and 35weight %, more preferably between 25 and 30 weight % is present as solidparticles.

In a preferred embodiment, the polymerization process is one where thereaction medium comprises a hydrocarbon fluid (regardless of whether thefluid act as solvent or diluent) and one or more fluorocarbons are addedto the polymerization reactor in an amount effective to induceprecipitation of polymers produced. The precipitated polymers remain insolid state in droplet or particle forms during the polymerization.Preferably upon addition of a fluorocarbon at least 0.1 weight % of thereaction medium is polymer present as solid particles, preferably atleast 5 weight % of the reaction medium is present as solid particles,more preferably between 5 and 50 weight % is present as solid particles,more preferably between 10 and 45 weight %, more preferably between 15and 40 weight %, more preferably between 20 and 35 weight %, morepreferably between 25 and 30 weight % is present as solid particles.Preferred hydrocarbons include aliphatic or aromatic hydrocarbon fluidsincluding, for example, saturated hydrocarbons containing from 3 to 8carbon atoms, such as propane, n-butane, isobutane, cyclopentane,n-pentane, isopentane, neopentane, n-hexane, isohexane, octane,isooctane, cyclohexane and other saturated C₆ to C₈ hydrocarbons.Particularly preferred hydrocarbon fluids include desulphurized lightvirgin naphtha and alkanes, such as propane, isobutane, mixed butanes,hexane, pentane, isopentane, cyclohexane, isooctane, and octane.Likewise one may also use mixtures of C3 to C20 paraffins andisoparaffins, preferably paraffinic/isoparrifinic mixtures of C4, C5 andor C6 alkanes. Octanes and hexanes are also preferred.

In a preferred embodiment, the fluorocarbons are present in thepolymerization media at 5 to 99 volume %, based upon the volume of themedia, preferably the fluorocarbons are present at 10 to 90 volume %,preferably at 20 to 80 more preferably at 20 to 60 volume %, morepreferably at 30 to 50 volume %. For purposes of this invention and theclaims thereto polymerization media means the mixture of solvent/diluentand unreacted monomers.

In a preferred embodiment, the fluorocarbons are present in thepolymerization effluent at 5 to 99 volume %, based upon the volume ofthe effluent, preferably the fluorocarbons are present at 10 to 90volume %, preferably 15 to 80 volume %, more preferably at 20 to 70volume %, more preferably 20 to 50 volume %. For purposes of thisinvention and the claims thereto polymerization effluent means themixture of unreacted monomers, solvent/diluent, polymers produced andother additives introduced after polymerization reactor.

Fluorocarbons

The polymerization processes of this invention are preferably conductedin the presence of a perfluorocarbon (“PFC” or “PFC's”) or ahydrofluorocarbon (“HFC” or “HFC's”), collectively referred to as“fluorinated hydrocarbons” or “fluorocarbons” (“FC” or “FC's”). Inanother embodiment the polymerization process is conducted withoutfluorocarbon present and the fluorocarbon is added to the polymerizationeffluent after the polymerization reaction has stopped. In anotherembodiment the polymerization process is conducted in the presence offluorocarbon and additional fluorocarbon (which may be the same ordifferent from the first fluorocarbon) is added to the polymerizationeffluent after the polymerization reaction has exited the reactor and orthe polymerization reaction has stopped.

Fluorocarbons are defined to be compounds consisting essentially of atleast one carbon atom and at least one fluorine atom, and optionallyhydrogen atom(s). A perfluorocarbon is a compound consisting essentiallyof carbon atom and fluorine atom, and includes for example linearbranched or cyclic, C₁ to C₄₀ perfluoroalkanes. A hydrofluorocarbon is acompound consisting essentially of carbon, fluorine and hydrogen.Preferred HFC's include those represented by the formula:C_(x)H_(y)F_(z) wherein x is an integer from 1 to 40, alternatively from1 to 30, alternatively from 1 to 20, alternatively from 1 to 10,alternatively from 1 to 6, alternatively from 2 to 20 alternatively from3 to 10, alternatively from 3 to 6, most preferably from 1 to 3, whereiny is greater than or equal 0 and z is an integer and at least one, morepreferably, y and z are integers and at least one. In a preferredembodiment, z is 2 or more. For purposes of this invention and theclaims thereto, the terms hydrofluorocarbon and fluorocarbon do notinclude chlorofluorocarbons.

In one embodiment, a mixture of fluorocarbons are used in the process ofthe invention, preferably a mixture of a perfluorinated hydrocarbon anda hydrofluorocarbon, and more preferably a mixture of ahydrofluorocarbons. In yet another embodiment, the hydrofluorocarbon isbalanced or unbalanced in the number of fluorine atoms in the HFC used.In another embodiment, the fluorocarbon is not a perfluorinatedhydrocarbon.

Non-limiting examples of fluorocarbons useful in this invention includefluoromethane; difluoromethane; trifluoromethane; fluoroethane;1,1-difluoroethane; 1,2-difluoroethane; 1,1,1-trifluoroethane;1,1,2-trifluoroethane; 1,1,1,2-tetrafluoroethane;1,1,2,2-tetrafluoroethane; 1,1,1,2,2-pentafluoroethane; 1-fluoropropane;2-fluoropropane; 1,1-difluoropropane; 1,2-difluoropropane;1,3-difluoropropane; 2,2-difluoropropane; 1,1,1-trifluoropropane;1,1,2-trifluoropropane; 1,1,3-trifluoropropane; 1,2,2-trifluoropropane;1,2,3-trifluoropropane; 1,1,1,2-tetrafluoropropane;1,1,1,3-tetrafluoropropane; 1,1,2,2-tetrafluoropropane;1,1,2,3-tetrafluoropropane; 1,1,3,3-tetrafluoropropane;1,2,2,3-tetrafluoropropane; 1,1,1,2,2-pentafluoropropane;1,1,1,2,3-pentafluoropropane; 1,1,1,3,3-pentafluoropropane;1,1,2,2,3-pentafluoropropane; 1,1,2,3,3-pentafluoropropane;1,1,1,2,2,3-hexafluoropropane; 1,1,1,2,3,3-hexafluoropropane;1,1,1,3,3,3-hexafluoropropane; 1,1,1,2,2,3,3-heptafluoropropane;1,1,1,2,3,3,3-heptafluoropropane; 1-fluorobutane; 2-fluorobutane;1,1-difluorobutane; 1,2-difluorobutane; 1,3-difluorobutane;1,4-difluorobutane; 2,2-difluorobutane; 2,3-difluorobutane;1,1,1-trifluorobutane; 1,1,2-trifluorobutane; 1,1,3-trifluorobutane;1,1,4-trifluorobutane; 1,2,2-trifluorobutane; 1,2,3-trifluorobutane;1,3,3-trifluorobutane; 2,2,3-trifluorobutane; 1,1,1,2-tetrafluorobutane;1,1,1,3-tetrafluorobutane; 1,1,1,4-tetrafluorobutane;1,1,2,2-tetrafluorobutane; 1,1,2,3-tetrafluorobutane;1,1,2,4-tetrafluorobutane; 1,1,3,3-tetrafluorobutane;1,1,3,4-tetrafluorobutane; 1,1,4,4-tetrafluorobutane;1,2,2,3-tetrafluorobutane; 1,2,2,4-tetrafluorobutane;1,2,3,3-tetrafluorobutane; 1,2,3,4-tetrafluorobutane;2,2,3,3-tetrafluorobutane; 1,1,1,2,2-pentafluorobutane;1,1,1,2,3-pentafluorobutane; 1,1,1,2,4-pentafluorobutane;1,1,1,3,3-pentafluorobutane; 1,1,1,3,4-pentafluorobutane;1,1,1,4,4-pentafluorobutane; 1,1,2,2,3-pentafluorobutane;1,1,2,2,4-pentafluorobutane; 1,1,2,3,3-pentafluorobutane;1,1,2,4,4-pentafluorobutane; 1,1,3,3,4-pentafluorobutane;1,2,2,3,3-pentafluorobutane; 1,2,2,3,4-pentafluorobutane;1,1,1,2,2,3-hexafluorobutane; 1,1,1,2,2,4-hexafluorobutane;1,1,1,2,3,3-hexafluorobutane, 1,1,1,2,3,4-hexafluorobutane;1,1,1,2,4,4-hexafluorobutane; 1,1,1,3,3,4-hexafluorobutane;1,1,1,3,4,4-hexafluorobutane; 1,1,1,4,4,4-hexafluorobutane;1,1,2,2,3,3-hexafluorobutane; 1,1,2,2,3,4-hexafluorobutane;1,1,2,2,4,4-hexafluorobutane; 1,1,2,3,3,4-hexafluorobutane;1,1,2,3,4,4-hexafluorobutane; 1,2,2,3,3,4-hexafluorobutane;1,1,1,2,2,3,3-heptafluorobutane; 1,1,1,2,2,4,4-heptafluorobutane;1,1,1,2,2,3,4-heptafluorobutane; 1,1,1,2,3,3,4-heptafluorobutane;1,1,1,2,3,4,4-heptafluorobutane; 1,1,1,2,4,4,4-heptafluorobutane;1,1,1,3,3,4,4-heptafluorobutane; 1,1,1,2,2,3,3,4-octafluorobutane;1,1,1,2,2,3,4,4-octafluorobutane; 1,1,1,2,3,3,4,4-octafluorobutane;1,1,1,2,2,4,4,4-octafluorobutane; 1,1,1,2,3,4,4,4-octafluorobutane;1,1,1,2,2,3,3,4,4-nonafluorobutane; 1,1,1,2,2,3,4,4,4-nonafluorobutane;1-fluoro-2-methylpropane; 1,1-difluoro-2-methylpropane;1,3-difluoro-2-methylpropane; 1,1,1-trifluoro-2-methylpropane;1,1,3-trifluoro-2-methylpropane; 1,3-difluoro-2-(fluoromethyl)propane;1,1,1,3-tetrafluoro-2-methylpropane;1,1,3,3-tetrafluoro-2-methylpropane;1,1,3-trifluoro-2-(fluoromethyl)propane;1,1,1,3,3-pentafluoro-2-methylpropane;1,1,3,3-tetrafluoro-2-(fluoromethyl)propane;1,1,1,3-tetrafluoro-2-(fluoromethyl)propane; fluorocyclobutane;1,1-difluorocyclobutane; 1,2-difluorocyclobutane;1,3-difluorocyclobutane; 1,1,2-trifluorocyclobutane;1,1,3-trifluorocyclobutane; 1,2,3-trifluorocyclobutane;1,1,2,2-tetrafluorocyclobutane; 1,1,3,3-tetrafluorocyclobutane;1,1,2,2,3-pentafluorocyclobutane; 1,1,2,3,3-pentafluorocyclobutane;1,1,2,2,3,3-hexafluorocyclobutane; 1,1,2,2,3,4-hexafluorocyclobutane;1,1,2,3,3,4-hexafluorocyclobutane; 1,1,2,2,3,3,4-heptafluorocyclobutane.In addition to those fluorocarbons described herein, those fluorocarbonsdescribed in Raymond Will, et. al., CEH Marketing Report, Fluorocarbons,Pages 1-133, by the Chemical Economics Handbook-SRI International, April2001, which is fully incorporated herein by reference, are included.

In another preferred embodiment, the fluorocarbon(s) used in the processof the invention are selected from the group consisting ofdifluoromethane, trifluoromethane, 1,1-difluoroethane,1,1,1-trifluoroethane, and 1,1,1,2-tetrafluoroethane and mixturesthereof.

In one particularly preferred embodiment, the commercially availablefluorocarbons useful in the process of the invention include HFC-236fahaving the chemical name 1,1,1,3,3,3-hexafluoropropane, HFC-134a havingthe chemical name 1,1,1,2-tetrafluoroethane, HFC-245fa having thechemical name 1,1,1,3,3-pentafluoropropane, HFC-365mfc having thechemical name 1,1,1,3,3-pentafluorobutane, R-318 having the chemicalname octafluorocyclobutane, and HFC-43-10mee having the chemical name2,3-dihydrodecafluoropentane.

In another embodiment, the fluorocarbon is not a perfluorinated C4 toC10 alkane. In another embodiment, the fluorocarbon is notperfluorodecalin, perfluoroheptane, perfluorohexane,perfluoromethylcyclohexane, perfluorooctane,perfluoro-1,3-dimethylcyclohexane, perfluorononane, fluorobenzene, orperfluorotoluene. In a particularly preferred embodiment, thefluorocarbon consists essentially of hydrofluorocarbons.

In another embodiment the fluorocarbon is present at more than 1 weight%, based upon the weight of the fluorocarbon and any hydrocarbon solventpresent in the reactor, preferably greater than 3 weight %, preferablygreater than 5 weight %, preferably greater than 7 weight %, preferablygreater than 10 weight %, preferably greater than 15 weight %,preferably greater than 20 weight %, preferably greater than 25 weight%, preferably greater than 30 weight %, preferably greater than 35weight %, preferably greater than 40 weight %, preferably greater than50 weight %, preferably greater than 55 weight %, preferably greaterthan 60 weight %, preferably greater than 70 weight %, preferablygreater than 80 weight %, preferably greater than 90 weight %. Inanother embodiment the fluorocarbon is present at more than 1 weight %,based upon the weight of the fluorocarbons, monomers and any hydrocarbonsolvent present in the reactor, preferably greater than 3 weight %,preferably greater than 5 weight %, preferably greater than 7 weight %,preferably greater than 10 weight %, preferably greater than 15 weight%, preferably greater than 20 weight %, preferably greater than 25weight %, preferably greater than 30 weight %, preferably greater than35 weight %, preferably greater than 40 weight %, preferably greaterthan 50 weight %, preferably greater than 55 weight %, preferablygreater than 60 weight %, preferably greater than 70 weight %,preferably greater than 80 weight %, preferably greater than 90 weight%. In the event that the weight basis is not named for the weight %fluorocarbon, it shall be presumed to be based upon the total weight ofthe fluorocarbons, monomers and hydrocarbon solvents present in thereactor.

In another embodiment the fluorocarbon, preferably thehydrofluorocarbon, is present at more than 1 volume %, based upon thetotal volume of the fluorocarbon and any hydrocarbon solvent present inthe reactor, preferably greater than 3 volume %, preferably greater than5 volume %, preferably greater than 7 volume %, preferably greater than10 volume %, preferably greater than 15 volume %, preferably greaterthan 20 volume %, preferably greater than 25 volume %, preferablygreater than 30 volume %, preferably greater than 35 volume %,preferably greater than 40 volume %, preferably greater than 45 volume%, preferably greater than 50 volume %, preferably greater than 55volume %, preferably greater than 60 volume %, preferably greater than65 volume %.

In another embodiment the fluorocarbon is a blend of hydrofluorocarbonand perfluorocarbon and preferably the hydrofluorocarbon is present atmore than 1 volume %, based upon the total volume of the perfluorocarbonand the hydrofluorocarbon present in the reactor, (with the balancebeing made up by the perfluorocarbon) preferably greater than 3 volume%, preferably greater than 5 volume %, preferably greater than 7 volume%, preferably greater than 10 volume %, preferably greater than 15volume %, preferably greater than 20 volume %, preferably greater than25 volume %, preferably greater than 30 volume %, preferably greaterthan 35 volume %, preferably greater than 40 volume %, preferablygreater than 45 volume %, preferably greater than 50 volume %,preferably greater than 55 volume %, preferably greater than 60 volume%, preferably greater than 65 volume %.

In yet another embodiment, the fluorocarbons of the invention have aweight average molecular weight (Mw) greater than 30 a.m.u., preferablygreater than 35 a.m.u, and more preferably greater than 40 a.m.u. Inanother embodiment, the fluorocarbons of the invention have a Mw greaterthan 60 a.m.u, preferably greater than 65 a.m.u, even more preferablygreater than 70 a.m.u, and most preferably greater than 80 a.m.u. Instill another embodiment, the fluorocarbons of the invention have a Mwgreater than 90 a.m.u, preferably greater than 100 a.m.u, even morepreferably greater than 135 a.m.u, and most preferably greater than 150a.m.u. In another embodiment, the fluorocarbons of the invention have aMw greater than 140 a.m.u, preferably greater than 150 a.m.u, morepreferably greater than 180 a.m.u, even more preferably greater than 200a.m.u, and most preferably greater than 225 a.m.u. In an embodiment, thefluorocarbons of the invention have a Mw in the range of from 90 a.m.uto 1000 a.m.u, preferably in the range of from 100 a.m.u to 500 a.m.u,more preferably in the range of from 100 a.m.u to 300 a.m.u, and mostpreferably in the range of from about 100 a.m.u to about 250 a.m.u.

In yet another embodiment, the fluorocarbons of the invention havenormal boiling point in the range of from about −100° C. up to thepolymerization temperature, preferably up to about 70° C., preferably upto about 85 to 115° C., preferably the normal boiling point of thefluorocarbons is in the range of from −80° C. to about 90° C., morepreferably from about −60° C. to about 85° C., and most preferably fromabout −50° C. to about 80° C. In an embodiment, the fluorocarbons of theinvention have normal boiling point greater than −50° C., preferablygreater than −50° C. to less than −10° C. In a further embodiment, thefluorocarbons of the invention have normal boiling point greater than−5° C., preferably greater than −5° C. to less than −20° C. In oneembodiment, the fluorocarbons of the invention have normal boiling pointgreater than 10° C., preferably greater than 10° C. to about 60° C.

In another embodiment, the fluorocarbons of the invention have a liquiddensity @ 20° C. (g/cc) less than 2 g/cc, preferably less than 1.6,preferably less than 1.5 g/cc, preferably less than 1.45 g/cc,preferably less than 1.40, and most preferably less than 1.20 g/cc.

In one embodiment, the fluorocarbons of the invention have a ΔHVaporization at the normal boiling point as measured by standardcalorimetry techniques in the range between 100 kJ/kg to less than 500kJ/kg, preferably in the range of from 110 kJ/kg to less than 450 kJ/kg,and most preferably in the range of from 120 kJ/kg to less than 400kJ/kg.

In another preferred embodiment, the fluorocarbons of the invention haveany combination of two or more of the aforementioned Mw, normal boilingpoint, ΔH Vaporization, and liquid density values and ranges. In apreferred embodiment, the fluorocarbons useful in the process of theinvention have a Mw greater than 30 a.m.u, preferably greater than 40a.m.u, and a liquid density less than 2.00 g/cc, preferably less than1.8 g/cc. In yet another preferred embodiment, the fluorocarbons usefulin the process of the invention have a liquid density less than 1.9g/cc, preferably less than 1.8 g/cc, and a normal boiling point greaterthan −100° C., preferably greater than −50° C. up to the polymerizationtemperature of the process, (such as up to 115° C.), preferably lessthan 100° C., and more preferably less than 90° C., and most preferablyless than 60° C., and optionally a ΔH Vaporization in the range from 120kj/kg to 400 kj/kg.

In another embodiment the fluorocarbons are used in combination with oneor more hydrocarbon solvents. Preferably, the hydrocarbon solvent is analiphatic or aromatic hydrocarbon fluids. Examples of suitable,preferably inert, solvents include, for example, saturated hydrocarbonscontaining from 1 to 10, preferably 3 to 8 carbon atoms, such aspropane, n-butane, isobutane, n-pentane, isopentane, neopentane,n-hexane, isohexane, cyclohexane and other saturated C₆ to C₈hydrocarbons. Preferred hydrocarbon fluids also include desulphurizedlight virgin naphtha and alkanes (preferably C1 to C8 alkanes), such aspropane, isobutane, mixed butanes, hexane, pentane, isopentane,cyclohexane and octane. Likewise one may also use mixtures of C3 to C20paraffins and isoparaffins, preferably paraffinic/isoparrifinic mixturesof C4, C5 and or C6 alkanes.

In another embodiment, the fluorocarbon fluid is selected based upon itssolubility or lack thereof in a particular polymer being produced.Preferred fluorocarbons have little to no solubility in the polymer.Solubility in the polymer is measured by forming the polymer into a filmof thickness between 50 and 100 microns, then soaking it in fluorocarbon(enough to cover the film) for 4 hours at the relevant desiredpolymerization temperature and pressure in a sealed container or vessel.The film is removed from the fluorocarbon, exposed for 90 seconds toevaporate excess fluorocarbon from the surface of the film, and weighed.The mass uptake is defined as the percentage increase in the film weightafter soaking. The fluorocarbon or fluorocarbon mixture is selected sothat the polymer has a mass uptake of less than 4 wt %, preferably lessthan 3 wt %, more preferably less than 2 wt %, even more preferably lessthan 1 wt %, and most preferably less than 0.5 wt %.

In a preferred embodiment, the fluorocarbon(s) or mixtures thereof,preferably, the HFC's or mixtures thereof, are selected such that thepolymer melting temperature Tm is reduced (or depressed) by not morethan 15° C. by the presence of the fluorocarbon. The depression of thepolymer melting temperature ΔTm is determined by first measuring themelting temperature of a polymer by differential scanning calorimetry(DSC), and then comparing this to a similar measurement on a sample ofthe same polymer that has been soaked with the fluorocarbon for fourhours. In general, the melting temperature of the soaked polymer will belower than that of the dry polymer. The difference in these measurementsis taken as the melting point depression ΔTm. Higher concentrations ofdissolved materials in the polymer cause larger depressions in thepolymer melting temperature (i.e. higher values of ΔTm). A suitable DSCtechnique for determining the melting point depression is described by,P. V. Hemmingsen, “Phase Equilibria in Polyethylene Systems”, Ph.DThesis, Norwegian University of Science and Technology, March 2000,which is incorporated herein by reference. (A preferred set ofconditions for conducting the tests are summarized on Page 112 of thisreference.) The polymer melting temperature is first measured with drypolymer, and then repeated with the polymer immersed in liquid (thefluorocarbon to be evaluated). As described in the reference above, itis important to ensure that the second part of the test, conducted inthe presence of the liquid, is done in a sealed container so that theliquid is not flashed during the test, which could introduceexperimental error. In one embodiment, the ΔTm is less than 12° C.,preferably less than 10° C., preferably less than 8° C., more preferablyless than 6° C., and most preferably less than 4° C. In anotherembodiment, the measured ΔTm is less than 5° C., preferably less than 4°C., more preferably less than 3° C., even more preferably less than 2°C., and most preferably less than 1° C.

In a preferred embodiment, the fluorocarbon(s) or mixtures thereof,preferably, the fluorocarbon or mixtures thereof, are selected such thatthese are miscible to the hydrocarbon solvent and liquid monomers when amixture is used. By miscible is meant that the FC and the hydrocarbonmixture will not have liquid phase separation. Liquid phase separationis determined by mixing a fluorocarbon and a hydrocarbon in a vesselwith sight glass at polymerization conditions, then visually observingif phase separation occurs after vigorous mixing for five minutes.

In another embodiment, the fluorocarbon(s) or mixtures thereof,preferably, the fluorocarbon or mixtures thereof, are selected such thatthese are immiscible in the hydrocarbon solvent and liquid monomers whena mixture is used. By immiscible is meant that the FC and thehydrocarbon mixture will have liquid-liquid phase separation. Thehydrocarbon, monomers and catalyst preferably remain in one liquidphase, while the fluorocarbons stay in another liquid phase. Preferably,with mixing, the liquid phase with hydrocarbon, monomers and catalystforms droplets dispersed in the fluorocarbon phase. While not wishing tobe bound by theory, it is believed that the dispersed droplets may actas micro-reactors where polymerization takes place.

In another embodiment, the fluorocarbon is selected such that thesolvency of reaction medium decreases to an extent to inducepolymer-solvent phase separation. While not wishing to be bound bytheory, it is believed that the polymerization then takes place at theinterface of polymer droplets. For polymers with fast crystallization,simultaneous polymerization and crystallization may take place.Successive polymerization and crystallization may occur for polymerswith slow crystallization.

Ideally, the fluorocarbon is inert to the polymerization reaction. By“inert to the polymerization reaction” is meant that the fluorocarbondoes not react chemically with the, monomers, catalyst system or thecatalyst system components. (This is not to say that the physicalenvironment provided by an FC's does not influence the polymerizationreactions, in fact, it may do so to some extent, such as affectingactivity rates. However, it is meant to say that the FC's are notpresent as part of the catalyst system.)

Polymerization Process

For purposes of this invention and the claims thereto, by continuous ismeant a system that operates (or is intended to operate) withoutinterruption or cessation. For example a continuous process to produce apolymer would be one where the reactants are continually introduced intoone or more reactors and polymer product is continually withdrawn. In apreferred embodiment any of the polymerization process described hereinare a continuous process.

In a preferred embodiment, the catalyst systems described herein areused in a polymerization process to produce olefin polymers,particularly ethylene and or propylene based olefin polymers where thepolymer is produced such that it is present as a solute in thepolymerization media or polymerization effluent. Generally this involvespolymerization in a continuous reactor in which the polymer formed andthe starting monomer and catalyst materials supplied, are agitated toreduce or avoid concentration gradients and in which the monomer acts asdiluent or solvent or in which a hydrocarbon is used as a diluent orsolvent. Suitable processes typically operate at temperatures from 0 to350° C., preferably from 10 to 300° C., more preferably from 40 to 200,more preferably 50 to 180° C. and at pressures at pressures of 0.1 MPaor more, preferably 2 MPa or more. The upper pressure limit is notcritically constrained but typically can be 200 MPa or less, preferably,120 MPa or less. Temperature control in the reactor is generallyobtained by balancing the heat of polymerization and with reactorcooling by reactor jackets or cooling coils to cool the contents of thereactor, auto refrigeration, pre-chilled feeds, vaporization of liquidmedium (diluent, monomers or solvent) or combinations of all three.Adiabatic reactors with pre-chilled feeds may also be used. Preferably afluorocarbon is added to the polymerization reactor as a pure componentor a mixture with other fluorocarbon and/or hydrocarbon. The type andamount of fluorocarbon need to be sufficient so that the precipitationof polymers produced occurs when a mixture of fluorocarbon andhydrocarbon is used. The type and amount of fluorocarbon also need to beoptimized for the maximum catalyst productivity for a particular type ofpolymerization. The fluorocarbon can be also introduced as a catalystcarrier. The fluorocarbon can be introduced as a gas phase or as aliquid phase depending on the pressure and temperature. Advantageously,the fluorocarbon is kept in a liquid phase and introduced as a liquid.FC can be directly fed in the feed to the polymerization reactors or maybe introduced with catalyst or monomer streams. Likewise thefluorocarbon may be added at the reactor exit or during recoveryprocesses after the polymer has exited the reactor and the FC may be thesame or different as the FC added during the polymerization.

In a preferred embodiment, the polymerization process is a, steadystate, polymerization conducted in a well-mixed continuous feedpolymerization reactor or reactors in series or parallel configuration.A preferred process can be described as a continuous, non-batch processthat, in its steady state operation, is exemplified by removal ofamounts of polymer made per unit time, being substantially equal to theamount of polymer withdrawn from the reaction vessel per unit time. By“substantially equal” we intend that these amounts, polymer made perunit time, and polymer withdrawn per unit time, are in ratios of one toother, of from 0.9:1; or 0.95:1; or 0.97:1; or 1:1. In such a reactor,there will be a substantially homogeneous monomer distribution. At thesame time, the polymerization is accomplished in substantially singlestep or stage or in a single reactor, contrasted to multistage ormultiple reactors (two or more). These conditions preferably exist forsubstantially all of the time the copolymer is produced. In such aprocess the fluorocarbon is preferably injected into the first reactorfeed, however the FC may also be injected into the reactor(s) directly.

In another preferred embodiment, the following procedure is carried outto obtain a copolymer, preferably comprising propylene and ethylene. Ina stirred-tank reactor propylene monomer is introduced continuouslytogether with solvent, fluorocarbon and ethylene monomer. The reactorcontains a liquid phase composed substantially of fluorocarbon, andethylene and propylene monomers together with any solvent or additionaldiluent. If desired, a small amount of a “H”-branch inducing diene suchas norbornadiene, 1,7-octadiene or 1,9-decadiene may also be added. Thetransition metal compound and activator are continuously introduced inthe reactor liquid phase. The reactor temperature and pressure may becontrolled by adjusting the solvent/monomer ratio, the catalyst additionrate, as well as by cooling or heating coils, jackets or both.Preferably the polymerization rate is controlled by the rate of catalystaddition. Typically, the ethylene content of the polymer product can bedetermined by the ratio of ethylene to propylene in the reactor, whichis controlled by manipulating the respective feed rates of thesecomponents to the reactor. The polymer product molecular weight ispreferably controlled by controlling other polymerization variables suchas the temperature, monomer concentration, or by a stream of hydrogenintroduced to the reactor, as is known in the art. The reactor effluentis contacted with a catalyst kill agent, such as water. The polymersolution is then optionally heated, and the polymer product is recoveredby flashing off unreacted gaseous ethylene and propylene andfluorocarbon as well as residual solvent or diluent at reduced pressure,and, if necessary, conducting further devolatilization in equipment suchas a devolatilizing extruder or other devolatilizing equipment operatedat reduced pressure.

For a propylene homo- or co-polymerization process conducted in thepresence of hydrocarbon diluent or solvent in addition to thefluorocarbon, especially a continuous polymerization, preferred rangesof propylene concentration at steady state are from about 0.05 weightpercent of the total reactor contents to about 50 weight percent of thetotal reactor contents, more preferably from about 0.5 weight percent ofthe total reactor contents to about 30 weight percent of the totalreactor contents, and most preferably from about 1 weight percent of thetotal reactor contents to about 25 weight percent of the total reactorcontents. The preferred range of polymer concentration (otherwise knownas % solids) is from about 3% of the reactor contents by weight to about45% of the reactor contents or higher, more preferably from about 10% ofthe reactor contents to about 40% of the reactor contents, and mostpreferably from about 15% of the reactor contents to about 40% of thereactor contents.

Preferably in a continuous process, the mean residence time of thecatalyst and polymer in the reactor generally is from 5 minutes to 8hours, and preferably from 10 minutes to 6 hours, more preferably fromten minutes to one hour. In some embodiments, comonomer (such asethylene) is added to the reaction vessel in an amount to maintain adifferential pressure in excess of the combined vapor pressure of themain monomer (such as a propylene) and any optional diene monomerspresent.

In another embodiment, the polymerization process is carried out with apressure of ethylene of from 10 to 2000 psi (70 to 14000 kPa), mostpreferably from 40 to 800 psi (280 to 5440 kPa). The polymerization isgenerally conducted at a temperature of from 25 to 350° C., preferablyfrom 75 to 300° C., and most preferably from greater than 95 to 250° C.

In another preferred embodiment, a process for producing a propylenehomopolymer or copolymer of propylene with at least one additionalolefinic monomer selected from ethylene or C4 to C20 alpha-olefinscomprises the following steps: 1) providing controlled addition of atransition metal compound to a reactor, including an activator andoptionally a scavenger component; 2) continuously feeding propylene andoptionally one or more additional olefinic monomers independentlyselected from ethylene or C4 to C20 alpha-olefins into the reactor,optionally with a solvent or diluent, and optionally with a controlledamount of hydrogen; 3) feeding fluorocarbon into the polymerizationreactor; and 4) recovering the polymer product. Preferably, the processis a continuous process that may or may not have hydrocarbon solvent ordiluent present in the reaction medium. Preferred ranges of ethyleneconcentration at steady state are from less than about 0.02 weightpercent of the total reactor contents to about 5 weight percent of thetotal reactor contents, and the preferred range of polymer concentrationis from about 10% of the reactor contents by weight to about 45% of thereactor contents or higher. The activators and optional scavengercomponents in the process can be independently mixed with the catalystcomponent before introduction into the reactor, or they may eachindependently be fed into the reactor using separate streams, resultingin “in reactor” activation. Scavenger components are known in the artand include, but are not limited to, alkyl aluminum compounds, includingalumoxanes. Examples of scavengers include, but are not limited to,trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trioctylaluminum, methylalumoxane (MAO), and other alumoxanes including, but notlimited to, MMAO3A. MMAO-7, PMAO-IP (all available from Akzo Nobel).Likewise, the fluorocarbons may be introduced into the reactor as amixture with one or more catalyst system components or a scavenger.

In another preferred embodiment, a process for producing an ethylenehomopolymer or copolymer of ethylene with at least one additionalolefinic monomer selected from C3 to C20 alpha-olefins comprises thefollowing steps: 1) providing controlled addition of a transition metalcompound to a reactor, including an activator and optionally a scavengercomponent; 2) continuously feeding ethylene and optionally one or moreadditional olefinic monomers independently selected from C3 to C20alpha-olefins into the reactor, optionally with a solvent or diluent,and optionally with a controlled amount of hydrogen; 3) feedingfluorocarbon into the polymerization reactor; and 4) recovering thepolymer product. Preferably, the process is a continuous process thatmay or may not have hydrocarbon solvent or diluent present in thereaction medium. Preferred ranges of comonomer concentration at steadystate are from less than about 0.02 weight percent of the total reactorcontents to about 5 weight percent of the total reactor contents, andthe preferred range of polymer concentration is from about 10% of thereactor contents by weight to about 45% of the reactor contents orhigher. The activators and optional scavenger components in the processcan be independently mixed with the catalyst component beforeintroduction into the reactor, or they may each independently be fedinto the reactor using separate streams, resulting in “in reactor”activation. Scavenger components are known in the art and include, butare not limited to, alkyl aluminum compounds, including alumoxanes.Examples of scavengers include, but are not limited to, trimethylaluminum, triethyl aluminum, triisobutyl aluminum, trioctyl aluminum,methylalumoxane (MAO), and other alumoxanes including, but not limitedto, MMAO3A. MMAO-7, PMAO-IP (all available from Akzo Nobel). Likewise,the fluorocarbons may be introduced into the reactor as a mixture withone or more catalyst system components or a scavenger.

The processes described herein can be carried out in a continuousstirred tank reactor, batch reactor, or plug flow reactor, or more thanone reactor operated in series or parallel. These reactors may have ormay not have internal cooling and the monomer feed may or may not berefrigerated. See the general disclosure of U.S. Pat. No. 5,001,205 forgeneral process conditions. See also, international application WO96/33227 and WO 97/22639. As previously noted, the processes describedabove may optionally use more than one reactor. The use of a secondreactor is especially useful in those embodiments in which an additionalcatalyst, especially a Ziegler-Natta or chrome catalyst, or by properselection of process conditions, including catalyst selection, polymerswith tailored properties can be produced. The cocatalysts and optionalscavenger components in the process can be independently mixed with thecatalyst component before introduction into the reactor, or they mayeach independently be fed into the reactor using separate streams,resulting in “in reactor” activation. Likewise, the fluorocarbons may beintroduced into the reactor as a mixture with one or more catalystsystem components or a scavenger. Each of the above processes may beemployed in single reactor, parallel or series reactor configurations.In series operation, the second reactor temperature is preferably higherthan the first reactor temperature. In parallel reactor operation, thetemperatures of the two reactors are independent. The pressure can varyfrom about 1 mm Hg to 2500 bar (250 MPa), preferably from 0.1 bar to1600 bar (0.1 kPa-160 MPa), most preferably from 1.0 to 500 bar (0.1MPa-50 MPa). The liquid processes comprise contacting olefin monomerswith the above described catalyst system in a suitable diluent orsolvent and allowing said monomers to react for a sufficient time toproduce the desired polymers. In multiple reactor processes thefluorocarbon may be introduced into one or all of the reactors. Inparticular, a fluorocarbon can be introduced into the first reactor, anda second fluorocarbon (which may be the same or different from the firstfluorocarbon) may be introduced into the second reactor. Likewise thefluorocarbon may be introduced in the first reactor alone or the secondreactor alone. In addition to the above, in multiple reactorconfigurations where there is a third, fourth or fifth reactor, thefluorocarbon may be introduced into all of the third, fourth and fifthreactors, none of the third, fourth and fifth reactors, just the thirdreactor, just the fourth reactor, just the fifth reactor, just the thirdand fourth reactors, just the third and fifth reactors, or just thefourth and fifth reactors.

Hydrocarbon fluids are suitable for use in the polymerizations of thisinvention as reaction media or parts of reaction media. Preferredhydrocarbon fluids include both aliphatic and aromatic fluids.Desulphurized light virgin naphtha and or alkanes, such as propane,isobutane, mixed butanes, hexane, pentane, isopentane, cyclohexane andoctane, are preferred.

In a preferred embodiment, a continuous solution polymerization is usedto produce copolymers of propylene and butene and or hexene. Thecopolymer may also optionally contain diene and or up to 10 weight %ethylene. The polymerization process utilizes two or more metallocenecatalysts as described below, preferably, dimethylsilyltetramethylcyclopentadienyl dodecylamide titanium dimethyl,rac-dimethylsilyl bis(2-methyl-4-phenyl indenyl)zirconium dimethyl,1,1′-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tertiary-butyl-9-fluorenyl)hafniumdimethyl, and or dimethylsilylbis(indenyl)hafnium dimethyl; combinedwith dimethylaniliniumtetrakis-(perfluorophenyl)borate as an activator.An organoaluminum compound, namely, tri-n-octylaluminum, tri-isobutylaluminum and or triethyl aluminum is preferably added as a scavenger tothe monomer feedstreams prior to introduction into the polymerizationprocess. The solution polymerization is conducted in a single, oroptionally in two, continuous stirred tank reactors connected in serieswith hexane, pentane or Isopar™ used as the solvent. The reactors may beoperated adiabatically or with a cooling loop. In addition, toluene maybe added to increase the solubility of the co-catalyst. The catalysts inhexane and the activator in toluene are introduced into the reactor orare introduced into the feed line and are mixed in line for a short timeprior to being fed into the reactor. The feed is transferred to thefirst reactor where the exothermic polymerization reaction is conductedadiabatically or with a coolant loop at a reaction temperature betweenabout 50° C. to about 220° C. The coolant loop, if present is, typicallykept at a temperature within 20° C. below the reactor temperature.Hydrogen gas may also be added to the reactors as a further molecularweight regulator. Scavenger (such as trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum) may be used if desired. If desired, polymer productis then transferred to a second reactor, which is also operatedadiabatically or with a coolant loop at a temperature between about 50°C. to 200° C. Additional monomers, solvent, catalyst, and activators canbe fed to the second reactor. The polymer content leaving the reactor(s)is typically from 8 to 50 weight percent. A heat exchanger then heatsthe polymer solution to a temperature of about 220° C. The polymersolution enters a low pressure separator vessel which operates at atemperature of about 200-230° C. and a pressure of 0 to 1 MPa andflashes the polymer solution to remove volatiles and to increase thepolymer content to about 76 to about 98 wt. %. The polymer rich solutionis then quenched with water, a low boiling alcohol or a carboxylic acidor its metal salt having from 2 to 21 carbon atoms. The volatiles fromthe flash vessel may then be recirculated to the reactor(s). A gear pumpat the bottom of the flash vessel drives the polymer rich solution to aflash devolatilizer. An gear pump is coupled to the end of the flashdevolatizer whereby the molten polymer material is transferred to astatic mixer where additives (0-20 wt % tackifier, 0-20 wt % oil, 0-20wt % LMWiPP, 0.1 to 10 wt % antioxidant, 0 to 10 wt % stabilizer, 0-10wt % wax, 0-10 wt % maleated PP wax) are combined with the moltenpolymer. Then the molten polymer may be fed to an underwater pelletizerwhere is cut into pellets, or the molten polymer may be packaged in drumcontainers. A spin dryer dries the polymer pellets which have a finalsolvent content of less than about 0.5 wt. %. A controlled volume of FCcomponents is mixed with the hydrocarbon solvent and monomers in thefeed preparation section before injection into the reactors. The rangeof FC's used is guided by a combination of:

(1) The boiling point of the FC is higher than ethylene and propylene(for example in the range 0 to 70° C.) so they co-condense and recyclewith the hydrocarbon solvent (hexanes) and no residual HFC remains inthe finished polymer product pellets; and

(2) The extent of fluorination of the FC's is such that they form asingle phase with the hexane solvent but impact the resulting solutionproperties such that any polymer formed in the reactor immediately phaseseparates into a polymer rich phase dispersed as droplets in thehydrocarbon/fluorocarbon continuous liquid phase in the reactor.

In a preferred embodiment, a continuous solution polymerization processis used to produce copolymers of ethylene/octene or ethylene/propyleneor terpolymers of ethylene/propylene/diene. For plastomers andelastomers the polymerization process preferably utilizes a metallocenecatalyst, namely,1,1′-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tertiary-butyl-9-fluorenyl)hafniumdimethyl with dimethylaniliniumtetrakis(pentafluorophenyl)borate as anactivator. An organoaluminum compound, namely, tri-n-octylaluminum, maybe added as a scavenger to the monomer feedstreams prior to introductioninto the polymerization process. For production of more crystallinepolymers, dimethylsilylbis(indenyl)hafnium dimethyl is used incombination with dimethylaniliniumtetrakis(pentafluorophenyl)borate.Preferably the solution polymerization is conducted in a single, oroptionally in two, continuous stirred tank reactors connected in serieswith hexane used as the solvent. In addition, toluene may be added toincrease the solubility of the co-catalyst. The feed is transferred tothe first reactor where the exothermic polymerization reaction isconducted adiabatically at a reaction temperature between about 50° C.to about 220° C. Hydrogen gas may also be added to the reactors as afurther molecular weight regulator. If desired, polymer product is thentransferred to the second reactor, which is also operated adiabaticallyat a temperature between about 50° C. to 200° C. Additional monomers,solvent, metallocene catalyst, and activators can be fed to the secondreactor. The polymer content leaving the second reactor is preferablyfrom 8 to 22 weight percent. A heat exchanger then heats the polymersolution to a temperature of about 220° C. The polymer solution is thenbrought to a Lower Critical Solution Temperature (LCST) liquid-liquidphase separator which causes the polymer solution to separate into twoliquid phases—an upper lean phase and a lower polymer-rich phase. Theupper lean phase contains about 70 wt. % of the solvent and the lowerpolymer rich phase contains about 30 wt. % polymer. The polymer solutionthen enters a low pressure separator vessel which operates at atemperature of about 150° C. and a pressure of 4-10 barg (400 to 1000Pa) and flashes the lower polymer rich phase to remove volatiles and toincrease the polymer content to about 76 wt. %. A gear pump at thebottom of the flash vessel drives the polymer rich solution to a Listdevolatilizer. An extruder is coupled to the end of the List devolatizerwhereby the polymer material is transferred to a gear pump which pushesthe polymer material through a screen pack. Then the polymer is cut intopellets and fed to a water bath. A spin dryer dries the polymer pelletswhich have a final solvent content of less than about 0.5 wt. %. Acontrolled volume of FC components is mixed with the hydrocarbon solvent(hexanes) and monomers in the feed preparation section before injectioninto the reactors. The range of FC's used is guided by a combination of:

1) The boiling point of the FC is higher than ethylene and propylene(for example in the range 0 to 70° C.) so they co-condense and recyclewith the hydrocarbon solvent (hexanes) in the distillation section (Alsothe anti-solvent effect of the FC's lowering the critical solution phasecloud point curve making more efficient separation in the liquid-liquidseparator possible. Preferably the FC's would separate with thehydrocarbon solvent in the polymer lean phase. Hence use of these FC'scould result in the operation of this critical solution separator atmilder conditions of temperature and pressure. Preferably there is noresidual HFC remains in the finished polymer product pellets); and

2) The extent of fluorination of the FC's is such that they form asingle phase with the hexane solvent but impact the resulting solutionproperties such that any polymer formed in the reactor immediately phaseseparates into a polymer rich phase dispersed as droplets in thehydrocarbon/fluorocarbon continuous liquid phase in the reactor. Inaddition their role as anti-solvent enables operation of the criticalphase liquid-liquid separator at milder conditions.

Addition of fluorocarbon into the effluent makes the polymer-solventphase separation at milder conditions (e.g., lower temperatures). Theprocess can be also simplified by replacing the LCST and associatedheating unit with a conventional flash tank when sufficient amount offluorocarbon is used.

EPDM polymers are commonly produced in stirred flow reactors of eitherone or more stages. For example, U.S. Pat. No. 3,678,019 discloses aone-stage reaction system in which a monomer mixture of ethylene, higheralpha-olefin and diene is fed into a reaction vessel along with aZiegler-Natta catalyst, a cocatalyst and aromatic hydrocarbon solvent.Similar processes are disclosed in U.S. Pat. Nos. 3,696,086 and3,725,364. In conventional multi-stage reactions, the ethylene, higheralpha-olefin and non-conjugated diene are added to each reactor tomaintain a relatively uniform composition of the terpolymer. One suchmulti-stage method is disclosed in U.S. Pat. No. 3,629,212. In apreferred embodiment, a terpolymer is prepared by (1) adding to a firstreactor solvent, from about 50 to 90 percent by weight of the totalethylene charge, from about 30 to 100 percent by weight of the totalhigher alpha-olefin charge, from about 30 to 100 percent by weight ofthe total Ziegler-Natta catalyst charge, from about 30 to 100 percent byweight of the total organoaluminum cocatalyst charge and non-conjugateddiene, (2) partially polymerizing a portion of the ethylene, higheralpha-olefin and diene in that first reactor to form a polymer cement(polymer dissolved in the solvent); (3) passing the reactor contentsincluding the polymer cement from the first reactor to a second reactorconnected in series with the first reactor; (4) adding ethylene to thesecond reactor along with an amount of non-conjugated diene such thatthe resultant polymerized weight percent diene content of the polymerfrom the first reactor is at least about 10 percent greater, on arelative basis, than the resultant polymerized weight percent dienecontent of the polymer from the second reactor; and (5) furtherpolymerizing the ethylene, higher alpha-olefin and non-conjugated dienein the second reactor. From about 50 to about 100 percent by weight ofthe total non-conjugated diene charge is added to the first reactor,preferably from about 80 to about 100 percent and most preferably, allof the non-conjugated diene charge is fed only into the first reactor.(For example, where the resultant non-conjugated diene content in thepolymer from the first reactor would be 6% and that from the secondreactor 5%, the relative difference in diene content of the two polymersis at least 10%; in this example it is 20% greater.) Typically, afterthe desired polymerization has been completed the contents of the secondor subsequent reactor is discharged, the polymerization reaction of thedischarged contents is terminated, and the terpolymer is collected andfinished. In another suitable arrangement, the reaction zones may bewithin a single reactor with horizontal baffles dividing the reactorinto two or more distinct zones for polymerization. In such anarrangement, separate feed inlets are provided for each reaction zone.The same sequence of adding solvent, monomers, catalyst and cocatalystis provided in each zone, as in the case of two separate reactors. Thus,in a two-stage reactor system such as the one shown in U.S. Pat. No.4,016,342, the process of the present invention can be performed bycontinuously feeding ethylene, C3 or higher alpha-olefin, non-conjugateddiene, solvent, catalyst and cocatalyst into the first stirred reactor.Without quenching or otherwise deactivating the catalyst components,except through attrition within the first reactor, the polymer cement isfed directly from the first reactor to the second reactor. Additionalethylene is fed continuously into the second reactor. Preferably, C3 orhigher alpha-olefin is also fed continuously into the second reactor.Some non-conjugated diene can also be added to the second or subsequentreactor in an amount such that the resulting polymerized weight percentdiene content of the terpolymer from the first or preceding reactor isat least about 10 percent greater, on a relative basis, than theresulting polymerized weight percent diene content of the polymer fromthe second or following reactor. The monomers are thus furtherpolymerized in the second reactor. Hydrogen, or other chain transferagents, may also be optionally fed to one or more reactors to controlpolymer molecular weight. Any known solvent for the reaction mixturethat is effective for the purpose can be used in conducting solutionpolymerizations in accordance with the present invention. For example,suitable solvents would be hydrocarbon solvents such as aliphatic,cycloaliphatic and aromatic hydrocarbon solvents, or halogenatedversions of such solvents. The preferred solvents are C₁₂ or lower,straight chain or branched chain, saturated hydrocarbons, C₅ to C₉saturated alicyclic or aromatic hydrocarbons or C₂ to C₆ halogenatedhydrocarbons. Most preferred are C₁₂ or lower, straight 11 chain orbranched chain hydrocarbons, particularly hexane. Nonlimitingillustrative examples of solvents are butane, pentane, hexane, heptane,cyclopentane, cyclohexane, cycloheptane, methyl cyclopentane, methylcyclohexane, isooctane, benzene, toluene, xylene, chloroform,chlorobenzenes, tetrachloroethylene, dichloroethane and trichloroethane.These processes are carried out in a mix-free reactor system (such as aplug flow reactor system), which is one in which substantially no mixingoccurs between portions of the reaction mixture that contain polymerchains initiated at different times. Suitable reactors are a continuousflow tubular or a stirred batch reactor. A tubular reactor is well knownand is designed to minimize mixing of the reactants in the direction offlow. As a result, reactant concentration will vary along the reactorlength. In contrast, the reaction mixture in a continuous flow stirredtank reactor (CFSTR) is blended with the incoming feed to produce asolution of essentially uniform composition everywhere in the reactor.Consequently, the growing chains in a portion of the reaction mixturewill have a variety of ages and thus a single CFSTR is not suitable forthe process of this invention. However, it is well known that 3 or morestirred tanks in series with all of the catalyst fed to the firstreactor can approximate the performance of a tubular reactor. A batchreactor is a suitable vessel, preferably equipped with adequateagitation, to which the catalyst, solvent, and monomer are added at thestart of the polymerization. The charge of reactants is then left topolymerize for a time long enough to produce the desired product. Foreconomic reasons, a tubular reactor is preferred to a batch reactor forcarrying out the processes of this invention. The desired polymer can beobtained if additional solvent and reactants (e.g., at least one of theethylene, alpha-olefin and diene) are added either along the length of atubular reactor or during the course of polymerization in a batchreactor. Operating in this fashion may be desirable in certaincircumstances to control the polymerization rate or polymer composition.However, it is necessary to add essentially all of the catalyst at theinlet of the tube or at the onset of batch reactor operation to meet therequirement that essentially all polymer chains are initiatedsimultaneously. If adiabatic reactor operation is used, the inlettemperature of the reactor feed could be about from −50° C. to 150° C.It is believed that the outlet temperature of the reaction mixture couldbe as high as about 200° C. The preferred maximum outlet temperature isabout 70° C. The most preferred maximum is about 50° C. In the absenceof reactor cooling, such as by a cooling jacket, to remove the heat ofpolymerization, it has been determined that the temperature of thereaction mixture will increase from reactor inlet to outlet by about 13°C. per weight percent of copolymer in the reaction mixture (weight ofcopolymer per weight of solvent). The residence time of the reactionmixture in the mix-free reactor (such as a plug flow reactor) can varyover a wide range from as low as about 1 second to as high as 3600seconds. A preferred minimum is about 10 seconds. The most preferredminimum is about 15 seconds. It is believed that the maximum could be ashigh as about 3600 seconds. A preferred maximum is about 1800 seconds.The most preferred maximum is about 900 seconds.

Choice of reactor temperature is dependent upon the effect oftemperature on catalyst deactivation rate. Temperatures should notexceed the point at which the concentration of catalyst in the secondreactor is insufficient to make the desired polymer component in thedesired amount. This temperature will be a function of the details ofthe catalyst system. In general, the first reactor temperature can varybetween 0-110° C. with 10-90° C. preferred and 20-70° C. most preferred.Second reactor temperatures will vary from 40-140° C., with 50-120° C.preferred and 60-110° C. most preferred. The reactors may be cooled byreactor jackets, cooling coils, auto refrigeration, pre-chilled feeds orcombinations of these. Adiabatic reactors with pre-chilled feeds arepreferred. This gives rise to a temperature difference between reactorswhich is helpful for controlling polymer molecular weight. Residencetime is the same or different in each reactor stage as set by reactorvolumes and flow rates. Residence time is defined as the average lengthof time reactants spend within a process vessel. The total residencetime, i.e. the total time spent in all reactors is preferably 2-90minutes and more preferably 5-40 minutes. Polymer composition iscontrolled by the amount of monomers fed to each reactor of the train.In a two reactor series unreacted monomers from the first reactor flowinto the second reactor and so the monomers added to the second reactorare just enough to adjust the composition of the feed to the desiredlevel, taking into account the monomer carry over. Depending on reactionconditions in the first reactor (catalyst concentration, temperature,monomer feed rates, etc.) a monomer may be in excess in the reactoroutlet relative to the amount required to make a certain composition inthe second reactor. Since it is not economically feasible to remove amonomer from the reaction mixture, situations like this should beavoided by adjusting reaction conditions. The polymer product can berecovered from solution at the completion of the polymerization by anyof the techniques well known in the art such as steam stripping followedby extrusion drying or by devolatilizing extrusion. Polymer molecularweight is controlled by reactor temperature, monomer concentration, andby the addition of chain transfer agents such as hydrogen. Withmetallocene catalysts, polymer molecular weight usually declines asreaction temperature increases. Adiabatic reactor operation in a tworeactor series produces a higher temperature in the second reactor thanthe first making it easier to make the low molecular weight component inthe second reactor. Molecular weight in the second reactor can befurther reduced and MWD broadened by adding hydrogen to the secondreactor. Hydrogen can also be added to the first reactor but becauseunreacted hydrogen will carry over to the second reactor the molecularweight of both polymer components will be decreased in this situationand the effect of hydrogen on MWD will be much less. A controlled volumeof FC components is mixed with the hydrocarbon solvent and monomers inthe feed preparation section before injection into the reactors. Therange of FC's used is guided by a combination of:

1) The boiling point if the FC is higher than ethylene and propylenes(such as in the range 0 to 70° C.) so that they co-condense and recyclewith the recovered hydrocarbon solvent (hexanes) in the hexanepurification tower (thus no residual FC remains in the finished polymerproduct); and

2) The extent of fluorination of the FC's is such that they form asingle phase with the hexane solvent but impact the resulting solutionproperties such that any polymer formed in the reactor immediately phaseseparates into a polymer rich phase dispersed as droplets in thehydrocarbon/fluorocarbon continuous liquid phase in the reactor.

In another embodiment, ethylene polymers and copolymers (preferablyethylene octene copolymers) are produced in a solution process at apressure of 2.5 to 7.0, preferably 3.0 to 6.2 MPa, a temperature of 130to 300° C., preferably 170 to 250° C., in a hydrocarbon solvent,preferably an isoparaffin solvent, such as ISOPAR E™ (which is anisoparaffin solvent having a pour point of −63° C., a distillation rangeof 117-136° C., a specific gravity of 0.72, a viscosity of 0.85 cSt at25° C., and less than 0.01 weight % aromatics, available from ExxonMobilChemical Company, in Houston, Tex.). In a particularly preferredembodiment, monomer (such as recycled or fresh ethylene compressed to2.6 to 7.0 MPa) is mixed with fresh comonomer, fresh solvent and anyrecycle solvent-comonomer blend. The total stream is cooled to about−150 to 50° C., preferably to about 10-20° C., and transferred to apolymerization reactor(s) via a feed pump (the feed is preferably cooledto help maintain a reactor outlet temperature of about 220 to 240° C.).Single or multiple reactors in series may be used. If multiple reactorsare used, it provides the opportunity for better control of heat removaland tailoring of product properties such as molecular weight, andmolecular weight distribution and allows higher conversion for highermolecular weight products. The system is preferably operated at lowresidence times, such as 3 to 20 minutes, preferably 5 to 12 minutes.Typically the system operates at 15 to 28% polymer in the solution,influenced principally by product melt index requirements and the impacton solution viscosity/mixing. Once removed from the reactor the meltsolution (effluent) is typically heated and devolatilized in a firstflash drum at 0.1 to 0.5 MPa. The residual polymer with some solvent,fluorocarbon and comonomer may be further heated and transferred to avacuum flash drum or vacuum falling strand evaporator for removal ofresidual volatiles operating at vacuum down to 20 mm Hg. The polymermelt from this vacuum vessel is finished in a static mixer or meltextruder to yield pellets. In a preferred embodiment, ethylene polymershaving densities up to 0.965 g/cc and ethylene octene copolymers below0.940 g/cc density are produced by this process. A controlled volume ofFC components is mixed with the hydrocarbon solvent and monomers in thefeed preparation section before injection into the reactors. The rangeof FC's used is guided by a combination of:

1) The boiling point of the FC is higher than ethylene so they areco-condensed with the hydrocarbon solvent and unreacted comonomer(octene) in the overhead of the recycle wax separation stripper towerbut lower than octane/octene so that no residual FC remains in thefinished polymer product pellets; and

2) The extent of fluorination of the FC's is such that they form asingle phase with the hexane solvent but impact the resulting solutionproperties such that any polymer formed in the reactor immediately phaseseparates into a polymer rich phase dispersed as droplets in thehydrocarbon/fluorocarbon continuous liquid phase in the reactor.

In another embodiment, ethylene polymers and copolymers (preferablyethylene octene copolymers) are produced in a solution process at apressure of 4.0 to 7.0, preferably 4.5 to 6.3 MPa, a temperature of 120to 300° C., preferably 125 to 235° C., in a hydrocarbon solvent,preferably an isoparaffin solvent, such as ISOPAR E™ (which is anisoparaffin solvent having a pour point of −63° C., a distillation rangeof 117-136° C., a specific gravity of 0.72, a viscosity of 0.85 cSt at25° C., and less than 0.01 weight % aromatics, available from ExxonMobilChemical Company, in Houston, Tex.). In a particularly preferredembodiment, monomer (such as recycled or fresh ethylene compressed to4.6 to 7.0 MPa) is mixed with fresh comonomer, fresh solvent and anyrecycle solvent-comonomer blend. The total stream is cooled to about−150 to 50° C., preferably to about 10-20° C., and transferred to apolymerization reactor(s) via a feed pump. These reactors are of a loopdesign fitted with one or two heat exchangers cooled by tempered waterto avoid crystallization deposition on the exchanger surface. A singleloop reactor or 2 loop reactors arranged either in series or parallelmay be used. If multiple reactors are used, it provides the opportunityfor better control of heat removal and tailoring of product propertiessuch as molecular weight, and molecular weight distribution. Freshmonomer, comonomer additional catalyst or another catalyst may beinjected in the second reactor when in series operation. In paralleloperation the conditions and even catalyst types may differ between thetwo reactors. Both reactor effluent solutions are combined beforeflashing and polymer recovery to allow efficient mixing of differingpolymer structures. The system is preferably operated at low residencetimes, such as 3 to 20 minutes, preferably 5 to 12 minutes. Typicallythe system operates at 15 to 28% polymer in the solution, influencedprincipally by product melt index requirements and the impact onsolution viscosity/mixing. Once removed from the reactor the meltsolution is typically heated and devolatilized in a first flash drum at0.1 to 0.5 MPa. The residual polymer with some solvent, fluorocarbon andcomonomer may be further heated and transferred to a vacuum flash drumor vacuum falling strand evaporator for removal of residual volatilesoperating at vacuum down to 20 mm Hg. The polymer melt from this vacuumvessel is finished in a static mixer or melt extruder to yield pellets.A controlled volume of FC components is mixed with the hydrocarbonsolvent and monomers in the feed preparation section before injectioninto the reactors. The range of FC's used is guided by a combination of:

1) The boiling point of the FC is higher than ethylene so are theyco-condensed with the hydrocarbon solvent and unreacted comonomer(octene) in the overhead of the recycle wax separation stripper towerbut lower than octane/octene so that no residual FC remains in thefinished polymer product pellets; and

2) The extent of fluorination of the FC's is such that they form asingle phase with the isooctane solvent but are present in a controlledquantity to avoid polymer precipitation in the polymerization reactorsand first flash vessel at operating conditions. Their impact on polymersolvation and hydrodynamic volume is such that the viscosity of an FCmodified solution is lower than that without FC for the same polymermolecular weight and concentration. In a preferred embodiment, ethylenepolymers having densities up to 0.965 g/cc and ethylene octenecopolymers below 0.940 g/cc down to 0.865 cc/g density are produced bythis process.

Ethylene with one or more olefins (C3 to C20) are mixed with aparaffinic. Solvent such as Isopar E and cooled to −40 to 0 C. Catalystcomponents are injected as solutions either directly into the reactor orjust before the reaction zone. The polymerization is carried out in oneor more reactors in series operating at pressures up to 100 MPa andtemperatures in the range 40 to 140 C. These reactors may be continuousstirred tanks or loop type with the ability for heat removal through thereactor wall or via a heat exchanger in the reactor loop. The polymersolution is continuously removed, heated to 150-240 C before entering alow pressure flash vessel at 0.1 to 0.5 MPa. The volatile materials arecondensed and recycled. The polymer cement is transferred to a vacuumflash system for removal of residual solvent, monomers and waxes and theresulting polymer melt is finished in a devolatilizing extruder. Duringthe transfer to the second flash stage a catalyst killer such as water,a low boiling alcohol or carboxylic acid is inject at levels sufficientto kill all remaining catalytic activity. Preferably a controlled volumeof FC components is mixed with the hydrocarbon solvent and monomers inthe feed preparation section before injection into the reactors. Therange of FC's used is guided by a combination of:

a) The boiling point of the FC is preferably higher than ethylene suchthat the FC's co-condensed with the hydrocarbon solvent and unreactedcomonomer (octene) in the overhead of the recycle wax separationstripper tower but lower than octane/octene so that no residual FCremains in the finished polymer product pellets; and or

b) The extent of fluorination of the FC's is such that they form asingle phase with the hexane solvent but impact the resulting solutionproperties such that any polymer formed in the reactor immediately phaseseparates into a polymer rich phase dispersed as droplets in thehydrocarbon/fluorocarbon continuous liquid phase in the reactor.

In another embodiment, polymerization of ethylene and an alpha olefinsuch as octene-1 is carried out in a single agitated liquid filledvessel under adiabatic conditions at a temperature between 150 and 250°C., and a pressure of 450 and 1400 psi (3.1 to 9.7 MPa) with ahydrocarbon solvent such as mixed hexane or desulphurized light virginnaphtha present at a residence time of 20 minutes or less, preferably 10minutes or less. This reactor effluent is heated and depressurized to0.1 to 0.5 MPa in a flash vessel where unreacted ethylene and mostsolvent and comonomer exits as vapor for recovery and recycle. Asolution of stabilizers in isopropanol is injected into the polymer meltto kill the catalyst. This mixture is then pumped to either adevolatilizing twin screw extruder operating at 20 mm Hg or passes afalling strand vacuum evaporator before being finished in a meltextruder. Both finishing methods remove residual comonomer, solvent andsome waxy product. Solvent, unreacted monomers and waxy side productsare condensed and the liquid is water washed to remove isopropanol andstripped to separate waxy materials. The hydrocarbons are dried andpurified over fixed bed adsorbents before recycling to the feedpreparation drum. This process preferably is used to producehomopolymers of ethylene and copolymers of ethylene and butene, pentene,hexene, heptene and or octene, preferably butene, hexene and or octene,having densities from 0.880 to 0.965 g/cc, preferably from 0.900 to0.965 g/cc and melt indices of 0.5 to 100 dg/min (ASTM 1238, conditionE). Preferably a controlled volume of FC components is mixed with thehydrocarbon solvent and monomers in the feed preparation section beforeinjection into the reactors. The range of FC's used is guided by acombination of:

1) The boiling point of the FC is higher than ethylene (such as in therange of 0 to 70° C.) so they co-condense and recycle with thehydrocarbon solvent (hexanes) leaving no residual HFC remains in thefinished polymer product pellets; and

2) The extent of fluorination of the FC's is such that they form asingle phase with the hexane solvent but impact the resulting solutionproperties such that any polymer formed in the reactor immediately phaseseparates into a polymer rich phase dispersed as droplets in thehydrocarbon/fluorocarbon continuous liquid phase in the reactor.

In another embodiment, polymerization is carried out in a single or inmultiple reactors at a temperature up to 300° C. and pressures up to2000 psi (13.8 MPa) using a hydrocarbon solvent such as cyclohexanewhere the feed stream does not have to be refrigerated, the residencetimes are 10 minutes or less, preferably 5 minutes or less, morepreferably 2 minutes or less to produce ethylene homopolymers andcopolymers of ethylene and butene and or hexene. The reactors may bestirred tank, tubular or a combination thereof. Generally the ethyleneis mixed with solvent and comonomer, pressurized and fed into thereactor along with the catalyst. After polymerization a catalystdeactivator may be added to the solution stream to deactivate thecatalyst. The deactivator and or deactivated catalyst may then beremoved down stream (by alumina beds, for example). Then the moltenpolymer stream is depressurized where solvent and monomer are flashedoff. Steam stripping of the final polymer melt may be carried out toremove waxes and any residual solvent and comonomers before finishingwith a melt extruder/pelletizer. In a preferred embodiment, multiplereactors, particularly a stirred tank in series with a tube, are used.Preferably a controlled volume of FC components is mixed with thehydrocarbon solvent and monomers in the feed preparation section beforeinjection into the reactors. The range of FC's used is guided by acombination of:

1) The boiling point of the FC is higher than ethylene (such as in therange of 0 to 70 degc) so they co-condense and recycle with thehydrocarbon solvent (cyclohexane) leaving no residual HFC remains in thefinished polymer product pellets; and

2) The extent of fluorination of the FC's is such that they form asingle phase with the hexane solvent but impact the resulting solutionproperties such that any polymer formed in the reactor immediately phaseseparates into a polymer rich phase dispersed as droplets in thehydrocarbon/fluorocarbon continuous liquid phase in the reactor.Alternatively, two continuous stirred tanks in series operating atpressures up to 180 MPa with a light hydrocarbon paraffinic solvent suchas propane, butane, pentane or hexane may be used with the possibilityto inject additional monomer, comonomer and catalyst into the secondreactor. The reactor effluent is heated, flashed first at low pressures,below 0.5 MPa and then at vacuum before finishing in an extruder. Insuch a system, a controlled volume of FC components is mixed with thehydrocarbon solvent and monomers in the feed preparation section beforeinjection into the reactors. The range of FC's used is guided by acombination of:

1) The boiling point of the FC is higher than ethylene so they are notlost with any process degassing, preferably the FC's should boil withthe process solvent having a boiling point lower than the solvent tominimize loss into the polymer product; and

2) The extent of fluorination of the FC's is such that they form asingle phase with the hexane solvent but impact the resulting solutionproperties such that any polymer formed in the reactor immediately phaseseparates into a polymer rich phase dispersed as droplets in thehydrocarbon/fluorocarbon continuous liquid phase in the reactor.

In any of the embodiments described herein the materials stripped orflashed off may be passed through activated carbon to remove all or partof the FC's.

Catalyst Components and Catalyst Systems

All polymerization catalysts including conventional-type transitionmetal catalysts are suitable for use in the polymerization process ofthe invention. The following is a non-limiting discussion of the variouspolymerization catalysts useful in the process of the invention.

Conventional-Type Transition Metal Catalysts

Conventional-type transition metal catalysts are those traditionalZiegler-Natta catalysts and Phillips-type chromium catalyst well knownin the art. Examples of conventional-type transition metal catalysts arediscussed in U.S. Pat. Nos. 4,115,639, 4,077,904 4,482,687, 4,564,605,4,721,763, 4,879,359 and 4,960,741 all of which are herein fullyincorporated by reference. The conventional-type transition metalcatalyst compounds that may be used in the present invention includetransition metal compounds from Groups 3 to 10, preferably 4 to 6 of thePeriodic Table of Elements.

These conventional-type transition metal catalysts may be represented bythe formula:MR_(x)  (I)where M is a metal from Groups 3 to 10, preferably Group 4, morepreferably titanium; R is a halogen or a hydrocarbyloxy group; and x isthe valence of the metal M, preferably x is 1, 2, 3 or 4, morepreferably x is 4. Non-limiting examples of R include alkoxy, phenoxy,bromide, chloride and fluoride. Non-limiting examples ofconventional-type transition metal catalysts where M is titanium includeTiCl₃, TiCl₄, TiBr₄, Ti(OC₂H₅)₃Cl, Ti(OC₂H₅)₃Cl₃, Ti(OC₄H₉)₃Cl,Ti(OC₃H₇)₂Cl₂, Ti(OC₂H₅)₂Br₂, TiCl₃.⅓AlCl₃ and Ti(OC₁₂H₂₅)Cl₃.

Conventional-type transition metal catalyst compounds based onmagnesium/titanium electron-donor complexes that are useful in theinvention are described in, for example, U.S. Pat. Nos. 4,302,565 and4,302,566, which are herein fully incorporate by reference. The MgTiCl₆(ethyl acetate)₄ derivative is particularly preferred. British PatentApplication 2,105,355, herein incorporated by reference, describesvarious conventional-type vanadium catalyst compounds. Non-limitingexamples of conventional-type vanadium catalyst compounds includevanadyl trihalide, alkoxy halides and alkoxides such as VOCl₃,VOCl₂(OBu) where Bu is butyl and VO(OC₂H₅)₃; vanadium tetra-halide andvanadium alkoxy halides such as VCl₄ and VCl₃(OBu); vanadium and vanadylacetyl acetonates and chloroacetyl acetonates such as V(AcAc)₃ andVOCl₂(AcAc) where (AcAc) is an acetyl acetonate. The preferredconventional-type vanadium catalyst compounds are VOCl₃, VCl₄ andVOCl₂—OR where R is a hydrocarbon radical, preferably a C₁ to C₁₀aliphatic or aromatic hydrocarbon radical such as ethyl, phenyl,isopropyl, butyl, propyl, n-butyl, iso-butyl, tertiary-butyl, hexyl,cyclohexyl, naphthyl, etc., and vanadium acetyl acetonates.

Conventional-type chromium catalyst compounds, often referred to asPhillips-type catalysts, suitable for use in the present inventioninclude CrO₃, chromocene, silyl chromate, chromyl chloride (CrO₂Cl₂),chromium-2-ethyl-hexanoate, chromium acetylacetonate (Cr(AcAc)₃), andthe like. Non-limiting examples are disclosed in U.S. Pat. Nos.2,285,721, 3,242,099 and 3,231,550, which are herein fully incorporatedby reference.

Still other conventional-type transition metal catalyst compounds andcatalyst systems suitable for use in the present invention are disclosedin U.S. Pat. Nos. 4,124,532, 4,302,565, 4,302,566 and 5,763,723 andpublished EP-A2 0 416 815 A2 and EP-A1 0 420 436, which are all hereinincorporated by reference.

The conventional-type transition metal catalysts of the invention mayalso have the general formula:M′_(t)M″X_(2t)Y_(u)E  (II)where M′ is Mg, Mn and/or Ca; t is a number from 0.5 to 2; M″ is atransition metal such as Ti, V and/or Zr; X is a halogen, preferably Cl,Br or I; Y may be the same or different and is halogen, alone or incombination with oxygen, —NR₂, —OR, —SR, —COOR, or —OSOOR, where R is ahydrocarbyl radical, in particular an alkyl, aryl, cycloalkyl orarylalkyl radical, acetylacetonate anion in an amount that satisfies thevalence state of M′; u is a number from 0.5 to 20; E is an electrondonor compound selected from the following classes of compounds: (a)esters of organic carboxylic acids; (b) alcohols; (c) ethers; (d)amines; (e) esters of carbonic acid; (f) nitriles; (g) phosphoramides,(h) esters of phosphoric and phosphorus acid, and (j) phosphorusoxy-chloride. Non-limiting examples of complexes satisfying the aboveformula include: MgTiCl₅.2CH₃COOC₂H₅, Mg₃Ti₂Cl₁₂.7CH₃COOC₂H₅,MgTiCl₅.6C₂H₅OH, MgTiCl₅.100CH₃OH, MgTiCl₅.tetrahydrofuran,MgTi₂Cl₁₂.7C₆H₅CN, Mg₃Ti₂Cl₁₂.6C₆H₅COOC₂H₅, MgTiCl₆.2CH₃COOC₂H₅,MgTiCl₆.6C₅H₅N, MnTiCl₅.4C₂H₅OH, MgTiCl₅(OCH₃).2CH₃COOC₂H₅,MgTiCl₅N(C₆H₅)₂.3CH₃COOC₂H₅, MgTiBr₂Cl₄.2(C₂H₅)₂O,Mg₃V₂Cl₁₂.7CH₃—COOC₂H₅, MgZrCl₆.4 tetrahydrofuran. Other catalysts mayinclude cationic catalysts such as AlCl₃, and other cobalt and ironcatalysts well known in the art.

Typically, these conventional-type transition metal catalyst compounds(excluding some conventional-type chromium catalyst compounds) areactivated with one or more of the conventional-type cocatalystsdescribed below.

In some embodiment, however, it is preferred that the catalyst systemnot comprise titanium tetrachloride, particularly not the combination ofTiCl₄ and aluminum alkyl (such as triethylaluminum), particularly whenthe FC is a perfluorocarbon. In situations where the catalyst istitanium tetrachloride, particularly the combination of TiCl₄ andaluminum alkyl (such as triethylaluminum) the FC is preferably ahydrofluorocarbon. In another embodiment, the catalyst is not a freeradical initiator, such as a peroxide.

Conventional-Type Cocatalysts

Conventional-type cocatalyst compounds for the above conventional-typetransition metal catalyst compounds may be represented by the formula:M³M⁴ _(v)X² _(c)R³ _(b-c)  (III)wherein M³ is a metal from Group 1, 2, 12 and 13 of the Periodic Tableof Elements; M⁴ is a metal of Group IA of the Periodic Table ofElements; v is a number from 0 to 1; each X² is any halogen; c is anumber from 0 to 3; each R³ is a monovalent hydrocarbon radical orhydrogen; b is a number from 1 to 4; and wherein b minus c is at least1.

Other conventional-type organometallic cocatalyst compounds for theabove conventional-type transition metal catalysts have the formula:M³R³ _(k)  (IV)where M³ is a Group 1, 2, 12 or 13 metal, such as lithium, sodium,beryllium, barium, boron, aluminum, zinc, cadmium, and gallium; k equals1, 2 or 3 depending upon the valency of M³ which valency in turnnormally depends upon the particular Group to which M³ belongs; and eachR³ may be any monovalent hydrocarbon radical.

Non-limiting examples of conventional-type organometallic cocatalystcompounds of Groups 1, 2, 12 and 13 useful with the conventional-typecatalyst compounds described above include methyllithium, butyllithium,dihexylmercury, butylmagnesium, diethylcadmium, benzylpotassium,diethylzinc, tri-n-butylaluminum, diisobutyl ethylboron, diethylcadmium,di-n-butylzinc and tri-n-amylboron, and, in particular, the aluminumalkyls, such as tri-hexyl-aluminum, triethylaluminum, trimethylaluminum,and tri-isobutylaluminum. Other conventional-type cocatalyst compoundsinclude mono-organohalides and hydrides of Group 2 metals, and mono- ordi-organohalides and hydrides of Group 13 metals. Non-limiting examplesof such conventional-type cocatalyst compounds includedi-isobutylaluminum bromide, isobutylboron dichloride, methyl magnesiumchloride, ethylberyllium chloride, ethylcalcium bromide,di-isobutylaluminum hydride, methylcadmium hydride, diethylboronhydride, hexylberyllium hydride, dipropylboron hydride, octylmagnesiumhydride, butylzinc hydride, dichloroboron hydride, di-bromo-aluminumhydride and bromocadmium hydride. Conventional-type organometalliccocatalyst compounds are known to those in the art, and a more completediscussion of these compounds may be found in U.S. Pat. Nos. 3,221,002and 5,093,415, which are herein fully incorporated by reference.

For purposes of this patent specification and appended claimsconventional-type transition metal catalyst compounds exclude thosebulky ligand metallocene-type catalyst compounds discussed below. Forpurposes of this patent specification and the appended claims the term“cocatalyst” refers to conventional-type cocatalysts orconventional-type organometallic cocatalyst compounds.

Bulky Ligand and Metallocene-Type Catalyst Compounds

Generally, polymerization catalysts useful in the invention include oneor more bulky ligand metallocene compounds (also referred to herein asmetallocenes). Typical bulky ligand metallocene compounds are generallydescribed as containing one or more bulky ligand(s) and one or moreleaving group(s) bonded to at least one metal atom. The bulky ligandsare generally represented by one or more open, acyclic, or fused ring(s)or ring system(s) or a combination thereof. These bulky ligands,preferably the ring(s) or ring system(s) are typically composed of atomsselected from Groups 13 to 16 atoms of the Periodic Table of Elements;preferably the atoms are selected from the group consisting of carbon,nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron andaluminum or a combination thereof. Most preferably, the ring(s) or ringsystem(s) are composed of carbon atoms such as, but not limited to,those cyclopentadienyl ligands or cyclopentadienyl-type ligandstructures or other similar functioning ligand structure such as apentadiene, a cyclooctatetraendiyl or an imide ligand. The metal atom ispreferably selected from Groups 3 through 15 and the lanthanide oractinide series of the Periodic Table of Elements. Preferably the metalis a transition metal from Groups 4 through 12, more preferably Groups4, 5 and 6, and most preferably the transition metal is from Group 4.

Exemplary of these bulky ligand metallocene-type catalyst compounds andcatalyst systems are described in for example, U.S. Pat. Nos. 4,530,914,4,871,705, 4,937,299, 5,017,714, 5,055,438, 5,096,867, 5,120,867,5,124,418, 5,198,401, 5,210,352, 5,229,478, 5,264,405, 5,278,264,5,278,119, 5,304,614, 5,324,800, 5,347,025, 5,350,723, 5,384,299,5,391,790, 5,391,789, 5,399,636, 5,408,017, 5,491,207, 5,455,366,5,534,473, 5,539,124, 5,554,775, 5,621,126, 5,684,098, 5,693,730,5,698,634, 5,710,297, 5,712,354, 5,714,427, 5,714,555, 5,728,641,5,728,839, 5,753,577, 5,767,209, 5,770,753 and 5,770,664 all of whichare herein fully incorporated by reference. Also, the disclosures ofEuropean publications EP-A-0 591 756, EP-A-0 520 732, EP-A-0 420 436,EP-B1 0 485 822, EP-B1 0 485 823, EP-A2-0 743 324 and EP-B1 0 518 092and PCT publications WO 91/04257, WO 92/00333, WO 93/08221, WO 93/08199,WO 94/01471, WO 96/20233, WO 97/15582, WO 97/19959, WO 97/46567, WO98/01455, WO 98/06759 and WO 98/011144 are all herein fully incorporatedby reference for purposes of describing typical bulky ligandmetallocene-type catalyst compounds and catalyst systems.

In one embodiment, the catalyst composition of the invention includesone or more bulky ligand metallocene catalyst compounds represented bythe formula:L^(A)L^(B)MQ_(n)  (V)where M is a metal atom from the Periodic Table of the Elements and maybe a Group 3 to 12 metal or from the lanthanide or actinide series ofthe Periodic Table of Elements, preferably M is a Group 4, 5 or 6transition metal, more preferably M is a Group 4 transition metal, evenmore preferably M is zirconium, hafnium or titanium. The bulky ligands,L^(A) and L^(B), are open, acyclic or fused ring(s) or ring system(s)and are any ancillary ligand system, including unsubstituted orsubstituted, cyclopentadienyl ligands or cyclopentadienyl-type ligands,heteroatom substituted and/or heteroatom containingcyclopentadienyl-type ligands. Non-limiting examples of bulky ligandsinclude cyclopentadienyl ligands, cyclopentaphenanthreneyl ligands,indenyl ligands, benzindenyl ligands, fluorenyl ligands,octahydrofluorenyl ligands, cyclooctatetraendiyl ligands,cyclopentacyclododecene ligands, azenyl ligands, azulene ligands,pentalene ligands, phosphoyl ligands, phosphinimine (WO 99/40125),pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzeneligands and the like, including hydrogenated versions thereof, forexample tetrahydroindenyl ligands. In one embodiment, L^(A) and L^(B)may be any other ligand structure capable of π-bonding to M. In yetanother embodiment, the atomic molecular weight (MW) of L^(A) or L^(B)exceeds 60 a.m.u., preferably greater than 65 a.m.u. In anotherembodiment, L^(A) and L^(B) may comprise one or more heteroatoms, forexample, nitrogen, silicon, boron, germanium, sulfur and phosphorous, incombination with carbon atoms to form an open, acyclic, or preferably afused, ring or ring system, for example, a hetero-cyclopentadienylancillary ligand. Other L^(A) and L^(B) bulky ligands include but arenot limited to bulky amides, phosphides, alkoxides, aryloxides, imides,carbolides, borollides, porphyrins, phthalocyanines, corrins and otherpolyazomacrocycles. Independently, each L^(A) and L^(B) may be the sameor different type of bulky ligand that is bonded to M. In one embodimentof Formula III only one of either L^(A) or L^(B) is present.

Independently, each L^(A) and L^(B) may be unsubstituted or substitutedwith a combination of substituent groups R. Non-limiting examples ofsubstituent groups R include one or more from the group selected fromhydrogen, or linear, branched alkyl radicals, or alkenyl radicals,alkynyl radicals, cycloalkyl radicals or aryl radicals, acyl radicals,aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals,dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonylradicals, carbomoyl radicals, alkyl- or dialkyl-carbamoyl radicals,acyloxy radicals, acylamino radicals, aroylamino radicals, straight,branched or cyclic, alkylene radicals, or combination thereof. In apreferred embodiment, substituent groups R have up to 50 non-hydrogenatoms, preferably from 1 to 30 carbon, that can also be substituted withhalogens or heteroatoms or the like. Non-limiting examples of alkylsubstituents R include methyl, ethyl, propyl, butyl, pentyl, hexyl,cyclopentyl, cyclohexyl, benzyl or phenyl groups and the like, includingall their isomers, for example tertiary butyl, isopropyl, and the like.Other hydrocarbyl radicals include fluoromethyl, fluoroethyl,difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbylsubstituted organometalloid radicals including trimethylsilyl,trimethylgermyl, methyldiethylsilyl and the like; andhalocarbyl-substituted organometalloid radicals includingtris(trifluoromethyl)-silyl, methyl-bis(difluoromethyl)silyl,bromomethyldimethylgermyl and the like; and disubstituted boron radicalsincluding dimethylboron for example; and disubstituted pnictogenradicals including dimethylamine, dimethylphosphine, diphenylamine,methylphenylphosphine, chalcogen radicals including methoxy, ethoxy,propoxy, phenoxy, methylsulfide and ethylsulfide. Non-hydrogensubstituents R include the atoms carbon, silicon, boron, aluminum,nitrogen, phosphorous, oxygen, tin, sulfur, germanium and the like,including olefins such as but not limited to olefinically unsaturatedsubstituents including vinyl-terminated ligands, for example but-3-enyl,prop-2-enyl, hex-5-enyl and the like. Also, at least two R groups,preferably two adjacent R groups, are joined to form a ring structurehaving from 3 to 30 atoms selected from carbon, nitrogen, oxygen,phosphorous, silicon, germanium, aluminum, boron or a combinationthereof.

Also, a substituent group R group such as 1-butanyl may form a carbonsigma bond to the metal M.

Other ligands may be bonded to the metal M, such as at least one leavinggroup Q. In one embodiment, Q is a monoanionic labile ligand having asigma-bond to M. Depending on the oxidation state of the metal, thevalue for n is 0, 1 or 2 such that Formula V above represents a neutralbulky ligand metallocene catalyst compound.

Non-limiting examples of Q ligands include weak bases such as amines,phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals havingfrom 1 to 20 carbon atoms, hydrides or halogens and the like or acombination thereof. In another embodiment, two or more Q's form a partof a fused ring or ring system. Other examples of Q ligands includethose substituents for R as described above and including cyclobutyl,cyclohexyl, heptyl, tolyl, trifluromethyl, tetramethylene,pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy,bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and thelike.

In another embodiment, the catalyst composition of the invention mayinclude one or more bulky ligand metallocene catalyst compounds whereL^(A) and L^(B) of Formula V are bridged to each other by at least onebridging group, A, as represented by:L^(A)AL^(B)MQ_(n)  (VI)wherein L^(A), L^(B), M, Q and n are as defined above. These compoundsof Formula VI are known as bridged, bulky ligand metallocene catalystcompounds. Non-limiting examples of bridging group A include bridginggroups containing at least one Group 13 to 16 atom, often referred to asa divalent moiety such as but not limited to at least one of a carbon,oxygen, nitrogen, silicon, aluminum, boron, germanium and tin atom or acombination thereof. Preferably bridging group A contains a carbon,silicon or germanium atom, most preferably A contains at least onesilicon atom or at least one carbon atom. The bridging group A may alsocontain substituent groups R as defined above including halogens andiron. Non-limiting examples of bridging group A may be represented byR′₂C, R′₂Si, R′₂Si R′₂Si, R′₂Ge, R′P, where R′ is independently, aradical group which is hydride, hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, hydrocarbyl-substitutedorganometalloid, halocarbyl-substituted organometalloid, disubstitutedboron, disubstituted pnictogen, substituted chalcogen, or halogen or twoor more R′ may be joined to form a ring or ring system. In oneembodiment, the bridged, bulky ligand metallocene catalyst compounds ofFormula VI have two or more bridging groups A (EP 664 301 B1).

In another embodiment, the bulky ligand metallocene catalyst compoundsare those where the R substituents on the bulky ligands L^(A) and L^(B)of Formulas V and VI are substituted with the same or different numberof substituents on each of the bulky ligands. In another embodiment, thebulky ligands L^(A) and L^(B) of Formulas V and VI are different fromeach other.

Other bulky ligand metallocene catalyst compounds and catalyst systemsuseful in the invention may include those described in U.S. Pat. Nos.5,064,802, 5,145,819, 5,149,819, 5,243,001, 5,239,022, 5,276,208,5,296,434, 5,321,106, 5,329,031, 5,304,614, 5,677,401, 5,723,398,5,753,578, 5,854,363, 5,856,547 5,858,903, 5,859,158, 5,900,517 and5,939,503 and PCT publications WO 93/08221, WO 93/08199, WO 95/07140, WO98/11144, WO 98/41530, WO 98/41529, WO 98/46650, WO 99/02540 and WO99/14221 and European publications EP-A-0 578 838, EP-A-0 638 595,EP-B-0 513 380, EP-A1-0 816 372, EP-A2-0 839 834, EP-B1-0 632 819,EP-B1-0 748 821 and EP-B1-0 757 996, all of which are herein fullyincorporated by reference.

In another embodiment, the catalyst compositions of the invention mayinclude bridged heteroatom, mono-bulky ligand metallocene compounds.These types of catalysts and catalyst systems are described in, forexample, PCT publication WO 92/00333, WO 94/07928, WO 91/04257, WO94/03506, WO96/00244, WO 97/15602 and WO 99/20637 and U.S. Pat. Nos.5,057,475, 5,096,867, 5,055,438, 5,198,401, 5,227,440 and 5,264,405 andEuropean publication EP-A-0 420 436, all of which are herein fullyincorporated by reference.

In another embodiment, the catalyst composition of the inventionincludes one or more bulky ligand metallocene catalyst compoundsrepresented by Formula VII:L^(C)AJMQ_(n)  (VII)where M is a Group 3 to 16 metal atom or a metal selected from the Groupof actinides and lanthanides of the Periodic Table of Elements,preferably M is a Group 4 to 12 transition metal, and more preferably Mis a Group 4, 5 or 6 transition metal, and most preferably M is a Group4 transition metal in any oxidation state, especially titanium; L^(C) isa substituted or unsubstituted bulky ligand bonded to M; J is bonded toM; A is bonded to J and L^(C); J is a heteroatom ancillary ligand; and Ais a bridging group; Q is a univalent anionic ligand; and n is theinteger 0, 1 or 2. In Formula VII above, L^(C), A and J form a fusedring system. In an embodiment, L^(C) of Formula V is as defined abovefor L^(A), A, M and Q of Formula VII are as defined above in Formula V.

In Formula VII, J is a heteroatom containing ligand in which J is anelement with a coordination number of three from Group 15 or an elementwith a coordination number of two from Group 16 of the Periodic Table ofElements. Preferably J contains a nitrogen, phosphorus, oxygen or sulfuratom with nitrogen being most preferred.

In a preferred embodiment, when the catalyst system comprises compoundsrepresented by Formula VII, the FC preferably is a hydrofluorocarbon.Preferably, when the catalyst system comprises compounds represented byFormula VII, the FC is not a perfluorocarbon.

In an embodiment of the invention, the bulky ligand metallocene catalystcompounds are heterocyclic ligand complexes where the bulky ligands, thering(s) or ring system(s), include one or more heteroatoms or acombination thereof. Non-limiting examples of heteroatoms include aGroup 13 to 16 element, preferably nitrogen, boron, sulfur, oxygen,aluminum, silicon, phosphorous and tin. Examples of these bulky ligandmetallocene catalyst compounds are described in WO 96/33202, WO96/34021, WO 97/17379 and WO 98/22486 and EP-A1-0 874 005 and U.S. Pat.Nos. 5,637,660, 5,539,124, 5,554,775, 5,756,611, 5,233,049, 5,744,417,and 5,856,258 all of which are herein incorporated by reference.

In one embodiment, the bulky ligand metallocene catalyst compounds arethose complexes known as transition metal catalysts based on bidentateligands containing pyridine or quinoline moieties, such as thosedescribed in U.S. application Ser. No. 09/103,620 filed Jun. 23, 1998,which is herein incorporated by reference. In another embodiment, thebulky ligand metallocene catalyst compounds are those described in PCTpublications WO 99/01481 and WO 98/42664, which are fully incorporatedherein by reference.

In another embodiment, the bulky ligand metallocene catalyst compound isa complex of a metal, preferably a transition metal, a bulky ligand,preferably a substituted or unsubstituted pi-bonded ligand, and one ormore heteroallyl moieties, such as those described in U.S. Pat. Nos.5,527,752 and 5,747,406 and EP-B1-0 735 057, all of which are hereinfully incorporated by reference.

In another embodiment, the catalyst composition of the inventionincludes one or more bulky ligand metallocene catalyst compounds isrepresented by Formula VIII:L^(D)MQ₂(YZ)X_(n)  (VIII)where M is a Group 3 to 16 metal, preferably a Group 4 to 12 transitionmetal, and most preferably a Group 4, 5 or 6 transition metal; L^(D) isa bulky ligand that is bonded to M; each Q is independently bonded to Mand Q₂(YZ) forms a ligand, preferably a unicharged polydentate ligand;or Q is a univalent anionic ligand also bonded to M; X is a univalentanionic group when n is 2 or X is a divalent anionic group when n is 1;n is 1 or 2.

In Formula VIII, L and M are as defined above for Formula V. Q is asdefined above for Formula V, preferably Q is selected from the groupconsisting of —O—, —NR—, —CR2— and —S—; Y is either C or S; Z isselected from the group consisting of —OR, —NR2, —CR3, —SR, —SiR3, —PR2,—H, and substituted or unsubstituted aryl groups, with the proviso thatwhen Q is —NR— then Z is selected from one of the group consisting of—OR, —NR2, —SR, —SiR3, —PR2 and —H; R is selected from a groupcontaining carbon, silicon, nitrogen, oxygen, and/or phosphorus,preferably where R is a hydrocarbon group containing from 1 to 20 carbonatoms, most preferably an alkyl, cycloalkyl, or an aryl group; n is aninteger from 1 to 4, preferably 1 or 2; X is a univalent anionic groupwhen n is 2 or X is a divalent anionic group when n is 1; preferably Xis a carbamate, carboxylate, or other heteroallyl moiety described bythe Q, Y and Z combination.

Still other useful catalysts include those multinuclear metallocenecatalysts as described in WO 99/20665 and 6,010,794, and transitionmetal metaaracyle structures described in EP 0 969 101 A2, which areherein incorporated herein by reference. Other metallocene catalystsinclude those described in EP 0 950 667 A1, double cross-linkedmetallocene catalysts (EP 0 970 074 A1), tethered metallocenes (EP 970963 A2) and those sulfonyl catalysts described in U.S. Pat. No.6,008,394, which are incorporated herein by reference.

It is also contemplated that in one embodiment the bulky ligandmetallocene catalysts, described above, include their structural oroptical or enantiomeric isomers (meso and racemic isomers, for examplesee U.S. Pat. No. 5,852,143, incorporated herein by reference) andmixtures thereof.

In another embodiment, the bulky ligand type metallocene-type catalystcompound is a complex of a transition metal, a substituted orunsubstituted pi-bonded ligand, and one or more heteroallyl moieties,such as those described in U.S. Pat. Nos. 5,527,752 and 5,747,406 andEP-B1-0 735 057, all of which are herein fully incorporated byreference.

The catalyst compositions of the invention may include one or morecomplexes known as transition metal catalysts based on bidentate ligandscontaining pyridine or quinoline moieties, such as those described inU.S. Pat. No. 6,103,657, which is herein incorporated by reference.

In one embodiment, these catalyst compounds are represented by theformula:((Z)XA_(t)(YJ))_(q)MQ_(n)  (IX)where M is a metal selected from Group 3 to 13 or lanthanide andactinide series of the Periodic Table of Elements; Q is bonded to M andeach Q is a monovalent, bivalent, or trivalent anion; X and Y are bondedto M; one or more of X and Y are heteroatoms, preferably both X and Yare heteroatoms; Y is contained in a heterocyclic ring J, where Jcomprises from 2 to 50 non-hydrogen atoms, preferably 2 to 30 carbonatoms; Z is bonded to X, where Z comprises 1 to 50 non-hydrogen atoms,preferably 1 to 50 carbon atoms, preferably Z is a cyclic groupcontaining 3 to 50 atoms, preferably 3 to 30 carbon atoms; t is 0 or 1;when t is 1, A is a bridging group joined to at least one of X, Y or J,preferably X and J; q is 1 or 2; n is an integer from 1 to 4 dependingon the oxidation state of M. In one embodiment, where X is oxygen orsulfur then Z is optional.

In another embodiment, where X is nitrogen or phosphorous then Z ispresent. In an embodiment, Z is preferably an aryl group, morepreferably a substituted aryl group.

In another embodiment of the invention the bulky ligand metallocene-typecatalyst compounds are those nitrogen containing heterocyclic ligandcomplexes, also known as transition metal catalysts based on bidentateligands containing pyridine or quinoline moieties, such as thosedescribed in WO 96/33202, WO 99/01481 and WO 98/42664 and U.S. Pat. No.5,637,660, which are herein all incorporated by reference.

It is within the scope of this invention, in one embodiment, thecatalyst compounds include complexes of Ni²⁺ and Pd²⁺ described in thearticles Johnson, et al., “New Pd(II)- and Ni(II)-Based Catalysts forPolymerization of Ethylene and a-Olefins”, J. Am. Chem. Soc. 1995, 117,6414-6415 and Johnson, et al., “Copolymerization of Ethylene andPropylene with Functionalized Vinyl Monomers by Palladium(II)Catalysts”, J. Am. Chem. Soc., 1996, 118, 267-268, and WO 96/23010published Aug. 1, 1996, WO 99/02472, U.S. Pat. Nos. 5,852,145, 5,866,663and 5,880,241, which are all herein fully incorporated by reference.These complexes can be either dialkyl ether adducts, or alkylatedreaction products of the described dihalide complexes that can beactivated to a cationic state by the activators of this inventiondescribed below.

Also included as bulky ligand metallocene-type catalyst compounds usefulherein are those diimine based ligands for Group 8 to 10 metal compoundsdisclosed in PCT publications WO 96/23010 and WO 97/48735 and Gibson,et. al., Chem. Comm., pp. 849-850 (1998), all of which are hereinincorporated by reference.

Other bulky ligand metallocene-type catalysts useful herein are thoseGroup 5 and 6 metal imido complexes described in EP-A2-0 816 384 andU.S. Pat. No. 5,851,945, which is incorporated herein by reference. Inaddition, bulky ligand metallocene-type catalysts useful herein includebridged bis(arylamido) Group 4 compounds described by D. H. McConville,et al., in Organometallics 1195, 14, 5478-5480, which is hereinincorporated by reference. Other bulky ligand metallocene-type catalystsuseful herein are described as bis(hydroxy aromatic nitrogen ligands) inU.S. Pat. No. 5,852,146, which is incorporated herein by reference.Other metallocene-type catalysts containing one or more Group 15 atomsuseful herein include those described in WO 98/46651, which is hereinincorporated herein by reference. Still another metallocene-type bulkyligand metallocene-type catalysts useful herein include thosemultinuclear bulky ligand metallocene-type catalysts as described in WO99/20665, which is incorporated herein by reference. In addition, usefulGroup 6 bulky ligand metallocene catalyst systems are described in U.S.Pat. No. 5,942,462, which is incorporated herein by reference.

It is contemplated in some embodiments, that the bulky ligands of themetallocene-type catalyst compounds of the invention described above maybe asymmetrically substituted in terms of additional substituents ortypes of substituents, and/or unbalanced in terms of the number ofadditional substituents on the bulky ligands or the bulky ligandsthemselves are different.

It is also contemplated that in one embodiment, the bulky ligandmetallocene-type catalysts of the invention include their structural oroptical or enantiomeric isomers (meso and racemic isomers) and mixturesthereof. In another embodiment the bulky ligand metallocene-typecompounds useful in the invention may be chiral and/or a bridged bulkyligand metallocene-type catalyst compound.

Mixed Catalysts

It is also within the scope of this invention that the above describedbulky ligand metallocene-type catalyst compounds can be combined withone or more of the conventional-type transition metal catalystscompounds with one or more co-catalysts or activators or activationmethods described above. For example, see U.S. Pat. Nos. 4,937,299,4,935,474, 5,281,679, 5,359,015, 5,470,811, and 5,719,241 all of whichare herein fully incorporated herein reference.

In another embodiment of the invention one or more bulky ligandmetallocene-type catalyst compounds or catalyst systems may be used incombination with one or more conventional-type catalyst compounds orcatalyst systems. Non-limiting examples of mixed catalysts and catalystsystems are described in U.S. Pat. Nos. 4,159,965, 4,325,837, 4,701,432,5,124,418, 5,077,255, 5,183,867, 5,391,660, 5,395,810, 5,691,264,5,723,399 and 5,767,031 and PCT Publication WO 96/23010 published Aug.1, 1996, all of which are herein fully incorporated by reference.

It is further contemplated that two or more conventional-type transitionmetal catalysts may be combined with one or more conventional-typecocatalysts. Non-limiting examples of mixed conventional-type transitionmetal catalysts are described in for example U.S. Pat. Nos. 4,154,701,4,210,559, 4,263,422, 4,672,096, 4,918,038, 5,198,400, 5,237,025,5,408,015 and 5,420,090, all of which are herein incorporated byreference.

Activator and Activation Methods

The above described polymerization catalyst, particularly bulky ligandmetallocene-type catalyst compounds, are typically activated in variousways to yield catalyst compounds having a vacant coordination site thatwill coordinate, insert, and polymerize olefin(s).

For the purposes of this invention, the term “activator” is defined tobe any compound which can activate any one of the catalyst compoundsdescribed herein by converting the neutral catalyst compound to acatalytically active catalyst cation compound. Non-limiting activators,for example, include alumoxanes, aluminum alkyls, ionizing activators,which may be neutral or ionic, and conventional-type cocatalysts.

Alumoxanes

In one embodiment, alumoxane activators are utilized as an activator inthe catalyst composition of the invention. Alumoxanes are generallyoligomeric compounds containing —Al(R)—O— subunits, where R is an alkylgroup. Non-limiting examples of alumoxanes include methylalumoxane(MAO), modified methylalumoxane (MMAO), ethylalumoxane andisobutylalumoxane. Alumoxanes may be produced by the hydrolysis of therespective trialkylaluminum compound. MMAO may be produced by thehydrolysis of trimethylaluminum and a higher trialkylaluminum such astriisobutylaluminum. MMAO's are generally more soluble in aliphaticsolvents and more stable during storage. There are a variety of methodsfor preparing alumoxane and modified alumoxanes, non-limiting examplesof which are described in U.S. Pat. Nos. 4,665,208, 4,952,540,5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463,4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,157,137,5,103,031, 5,391,793, 5,391,529, 5,693,838, 5,731,253, 5,731,451,5,744,656, 5,847,177, 5,854,166, 5,856,256 and 5,939,346 and Europeanpublications EP-A-0 561 476, EP-B1-0 279 586, EP-A-0 594-218 and EP-B1-0586 665, and PCT publications WO 94/10180 and WO 99/15534, all of whichare herein fully incorporated by reference. Another alumoxane is amodified methyl alumoxane (MMAO) cocatalyst type 3A (commerciallyavailable from Akzo Chemicals, Inc. under the trade name ModifiedMethylalumoxane type 3A, covered under U.S. Pat. No. 5,041,584).Aluminum Alkyl or organoaluminum compounds which may be utilized asactivators include trimethylaluminum, triethylaluminum,triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and thelike.

Ionizing Activators

It is within the scope of this invention to use an ionizing orstoichiometric activator, neutral or ionic, such as tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)boron, a trisperfluorophenyl boron metalloidprecursor or a trisperfluoronaphtyl boron metalloid precursor,polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Pat.No. 5,942,459) or combination thereof. It is also within the scope ofthis invention to use neutral or ionic activators alone or incombination with alumoxane or modified alumoxane activators.

Non-limiting examples of neutral stoichiometric activators includetri-substituted boron, tellurium, aluminum, gallium and indium ormixtures thereof. The three substituent groups are each independentlyselected from alkyls, alkenyls, halogen, substituted alkyls, aryls,arylhalides, alkoxy and halides. Preferably, the three groups areindependently selected from halogen, mono or multicyclic (includinghalosubstituted) aryls, alkyls, and alkenyl compounds and mixturesthereof, preferred are alkenyl groups having 1 to 20 carbon atoms, alkylgroups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbonatoms and aryl groups having 3 to 20 carbon atoms (including substitutedaryls). More preferably, the three groups are alkyls having 1 to 4carbon groups, phenyl, napthyl or mixtures thereof. Even morepreferably, the three groups are halogenated, preferably fluorinated,aryl groups. Most preferably, the neutral stoichiometric activator istrisperfluorophenyl boron or trisperfluoronapthyl boron.

“Substituted alkyl” refers to an alkyl as described in which one or morehydrogen atoms of the alkyl is replaced by another group such as ahalogen, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, andcombinations thereof. Examples of substituted alkyls include, forexample, benzyl, trifluoromethyl and the like.

Ionic stoichiometric activator compounds may contain an active proton,or some other cation associated with, but not coordinated to, or onlyloosely coordinated to, the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP-A-0 570982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 andEP-A-0 277 004, and U.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741,5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. patentapplication Ser. No. 08/285,380, filed Aug. 3, 1994, all of which areherein fully incorporated by reference.

In a preferred embodiment, the stoichiometric activators include acation and an anion component, and may be represented by the followingformula:(L−H)_(d) ⁺·(A^(d−))  (X)wherein: L is an neutral Lewis base; H is hydrogen; (L−H)⁺ is a Bronstedacid; A^(d−) is a non-coordinating anion having the charge d−; and d isan integer from 1 to 3. The cation component, (L−H)_(d) ⁺ may includeBronsted acids such as protons or protonated Lewis bases or reducibleCatalysts capable of protonating or abstracting a moiety, such as anakyl or aryl, from the bulky ligand metallocene or Group 15 containingtransition metal catalyst precursor, resulting in a cationic transitionmetal species.

The activating cation (L−H)_(d) ⁺ may be a Bronsted acid, capable ofdonating a proton to the transition metal catalytic precursor resultingin a transition metal cation, including ammoniums, oxoniums,phosphoniums, silyliums and mixtures thereof, preferably ammoniums ofmethylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline,methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline,p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine,triphenylphosphine, and diphenylphosphine, oxomiuns from ethers such asdimethyl ether diethyl ether, tetrahydrofuran and dioxane, sulfoniumsfrom thioethers, such as diethyl thioethers and tetrahydrothiophene andmixtures thereof. The activating cation (L−H)_(d) ⁺ may also be anabstracting moiety such as silver, carboniums, tropylium, carbeniums,ferroceniums and mixtures, preferably carboniums and ferroceniums. Mostpreferably (L−H)_(d) ⁺ is triphenyl carbonium.

The anion component A^(d−) includes those having the formula[M^(k+)Q_(n)]^(d−) wherein k is an integer from 1 to 3; n is an integerfrom 2-6; n−k=d; M is an element selected from Group 13 of the PeriodicTable of the Elements, preferably boron or aluminum, and Q isindependently a hydride, bridged or unbridged dialkylamido, halide,alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Qhaving up to 20 carbon atoms with the proviso that in not more than 1occurrence is Q a halide. Preferably, each Q is a fluorinatedhydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q isa fluorinated aryl group, and most preferably each Q is a pentafluorylaryl group. Examples of suitable A^(d−) also include diboron compoundsas disclosed in U.S. Pat. No. 5,447,895, which is fully incorporatedherein by reference.

Most preferably, the ionic stoichiometric activator (L−H)_(d) ⁺·(A^(d−))is N,N-dimethylanilinium tetra(perfluorophenyl)borate ortriphenylcarbenium tetra(perfluorophenyl)borate.

In one embodiment, an activation method using ionizing ionic compoundsnot containing an active proton but capable of producing a bulky ligandmetallocene catalyst cation and their non-coordinating anion are alsocontemplated, and are described in EP-A-0 426 637, EP-A-0 573 403 andU.S. Pat. No. 5,387,568, which are all herein incorporated by reference.

Additional Activators

Other activators include those described in PCT publication WO 98/07515such as tris(2,2′,2″-nonafluorobiphenyl)fluoroaluminate, whichpublication is fully incorporated herein by reference. Combinations ofactivators are also contemplated by the invention, for example,alumoxanes and ionizing activators in combinations, see for example,EP-B1 0 573 120, PCT publications WO 94/07928 and WO 95/14044 and U.S.Pat. Nos. 5,153,157 and 5,453,410 all of which are herein fullyincorporated by reference.

Other suitable activators are disclosed in WO 98/09996, incorporatedherein by reference, which describes activating bulky ligand metallocenecatalyst compounds with perchlorates, periodates and iodates includingtheir hydrates. WO 98/30602 and WO 98/30603, incorporated by reference,describe the use of lithium (2,2′-bisphenyl-ditrimethylsilicate).4THF asan activator for a bulky ligand metallocene catalyst compound. WO99/18135, incorporated herein by reference, describes the use oforgano-boron-aluminum activators. EP-B1-0 781 299 describes using asilylium salt in combination with a non-coordinating compatible anion.Also, methods of activation such as using radiation (see EP-B1-0 615 981herein incorporated by reference), electro-chemical oxidation, and thelike are also contemplated as activating methods for the purposes ofrendering the neutral bulky ligand metallocene catalyst compound orprecursor to a bulky ligand metallocene cation capable of polymerizingolefins.

Other activators or methods for activating a bulky ligand metallocenecatalyst compound are described in for example, U.S. Pat. Nos.5,849,852, 5,859,653 and 5,869,723 and WO 98/32775, WO 99/42467(dioctadecylmethylammonium-bis(tris(pentafluorophenyl)borane)benzimidazolide), which are herein incorporated by reference.

Another suitable ion forming, activating cocatalyst comprises a salt ofa cationic oxidizing agent and a noncoordinating, compatible anionrepresented by the formula:(OX^(e+))_(d)(A^(d−))_(e)  (XII)wherein: OX^(e+) is a cationic oxidizing agent having a charge of e+; eis an integer from 1 to 3; and A⁻, and d are as previously definedabove. Non-limiting examples of cationic oxidizing agents include:ferrocenium, hydrocarbyl-substituted ferrocenium, Ag⁺, or Pb⁺².Preferred embodiments of A^(d−) are those anions previously defined withrespect to the Bronsted acid containing activators, especiallytetrakis(pentafluorophenyl)borate.

It is within the scope of this invention that catalyst compounds can becombined one or more activators or activation methods described above.For example, a combination of activators have been described in U.S.Pat. Nos. 5,153,157 and 5,453,410, European publication EP-B1 0 573 120,and PCT publications WO 94/07928 and WO 95/14044. These documents alldiscuss the use of an alumoxane and an ionizing activator with a bulkyligand metallocene catalyst compound.

In a preferred embodiment, the catalyst systems of this invention arenot present on a support.

A preferred catalyst compound for use in this invention is dimethylsilylt-butyl-amido tetramethylcyclopentadienyl titanium dichloride,preferably activated with a noncoordinating anion such asdimethylaniliniumtetrakis(pentafluorophenyl)borate.

Monomers

In a preferred embodiment the processes of this invention are used topolymerize any unsaturated monomer or monomers. Preferred monomersinclude C₂ to C₁₀₀ olefins, preferably C₂ to C₆₀ olefins, preferably C₂to C₄₀ olefins preferably C₂ to C₂₀ olefins, preferably C₂ to C₁₂olefins. In some embodiments preferred monomers include linear, branchedor cyclic alpha-olefins, preferably C₂ to C₁₀₀ alpha-olefins, preferablyC₂ to C₆₀ alpha-olefins, preferably C₂ to C₄₀ alpha-olefins preferablyC₂ to C₂₀ alpha-olefins, preferably C₂ to C₁₂ alpha-olefins. Preferredolefin monomers may be one or more of ethylene, propylene, butene,pentene, hexene, heptene, octene, nonene, decene, dodecene,4-methylpentene-1,3-methylpentene-1,3,5,5-trimethylhexene-1, and5-ethylnonene-1.

In another embodiment the polymer produced herein is a copolymer of oneor more linear or branched C₃ to C₃₀ prochiral alpha-olefins or C₅ toC₃₀ ring containing olefins or combinations thereof capable of beingpolymerized by either stereospecific and non-stereospecific catalysts.Prochiral, as used herein, refers to monomers that favor the formationof isotactic or syndiotactic polymer when polymerized usingstereospecific catalyst(s).

Polymers produced according to this invention are olefin polymers or“polyolefins”. By olefin polymers is meant that at least 75 mole % ofthe polymer is made of hydrocarbon monomers, preferably at least 80 mole%, preferably at least 85 mole %, preferably at least 90 mole %,preferably at least 95 mole %, preferably at least 99 mole %. In aparticularly preferred embodiment, the polymers are 100 mole %hydrocarbon monomer. Hydrocarbon monomers are monomers made up of onlycarbon and hydrogen. In another embodiment of the invention up to 25 mol% of the polyolefin is derived from heteroatom containing monomers.Heteroatom containing monomers are hydrocarbon monomers where one ormore hydrogen atoms have been replaced by a heteroatom. In a preferredembodiment, the heteroatom is selected from the group consisting ofchlorine, bromine, oxygen, nitrogen, silicon and sulfur, preferably theheteroatom is selected from the group consisting of oxygen, nitrogen,silicon and sulfur, preferably the heteroatom is selected from the groupconsisting of oxygen and nitrogen, preferably oxygen. In a preferredembodiment, the heteroatom is not fluorine. In another embodiment of theinvention, the monomers to be polymerized are not fluormonomers.Fluoromonomers are defined to be hydrocarbon monomers where at least onehydrogen atom has been replaced by a fluorine atom. In anotherembodiment of the invention, the monomers to be polymerized are nothalomonomers. (By halomonomer is meant a hydrocarbon monomer where atleast one hydrogen atom is replaced by a halogen.) In another embodimentof the invention, the monomers to be polymerized are not vinyl aromatichydrocarbons. In another embodiment of the invention, the monomers to bepolymerized are preferably aliphatic or alicyclic hydrocarbons. (asdefined under “Hydrocarbon” in Hawley's Condensed Chemical Dictionary,13th edition, R. J. Lewis ed., John Wiley and Sons, New York, 1997). Inanother embodiment of the invention, the monomers to be polymerized arepreferably linear or branched alpha-olefins, preferably C2 to C40 linearor branched alpha-olefins, preferably C2 to C20 linear or branchedalpha-olefins, preferably ethylene, propylene, butene, pentene, hexene,heptene, octene, nonene, decene, undecene, dodecene, or mixturesthereof, more preferably ethylene, propylene, butene hexene and octene.

Preferred monomers may also include aromatic-group-containing monomerscontaining up to 30 carbon atoms. Suitable aromatic-group-containingmonomers comprise at least one aromatic structure, preferably from oneto three, more preferably a phenyl, indenyl, fluorenyl, or naphthylmoiety. The aromatic-group-containing monomer further comprises at leastone polymerizable double bond such that after polymerization, thearomatic structure will be pendant from the polymer backbone. Thearomatic-group containing monomer may further be substituted with one ormore hydrocarbyl groups including but not limited to C₁ to C₁₀ alkylgroups. Additionally two adjacent substitutions may be joined to form aring structure. Preferred aromatic-group-containing monomers contain atleast one aromatic structure appended to a polymerizable olefinicmoiety. Particularly preferred aromatic monomers include vinyltoluenes,vinylnaphthalene, allyl benzene, and indene, especially4-phenyl-1-butene and allyl benzene.

Non aromatic cyclic group containing monomers are also preferred. Thesemonomers can contain up to 30 carbon atoms. Suitable non-aromatic cyclicgroup containing monomers preferably have at least one polymerizableolefinic group that is either pendant on the cyclic structure or is partof the cyclic structure. The cyclic structure may also be furthersubstituted by one or more hydrocarbyl groups such as, but not limitedto, C₁ to C₁₀ alkyl groups. Preferred non-aromatic cyclic groupcontaining monomers include vinylcyclohexane, vinylcyclohexene,cyclopentadiene, cyclopentene, 4-methylcyclopentene, cyclohexene,4-methylcyclohexene, cyclobutene, vinyladamantane, norbornene,5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene,5-butylylnorbornene, 5-pentylnorbornene, 5-hexylnorbornene,5-heptylnorbornene, 5-octylnorbornene, 5-nonylnorbornene,5-decylnorbornene, 5-phenylnorbornene, vinylnorbornene, ethylidenenorbornene, 5,6-dimethylnorbornene, 5,6-dibutylnorbornene and the like.

Preferred diolefin monomers useful in this invention include anyhydrocarbon structure, preferably C₄ to C₃₀, having at least twounsaturated bonds, wherein at least one, typically two, of theunsaturated bonds are readily incorporated into a polymer by either astereospecific or a non-stereospecific catalyst(s). It is furtherpreferred that the diolefin monomers be selected from alpha-omega-dienemonomers (i.e. di-vinyl monomers). More preferably, the diolefinmonomers are linear di-vinyl monomers, most preferably those containingfrom 4 to 30 carbon atoms. Examples of preferred dienes includebutadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene,decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene,pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene,nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene,tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene,octacosadiene, nonacosadiene, triacontadiene, particularly preferreddienes include 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene,1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene,1,13-tetradecadiene, and low molecular weight polybutadienes (Mw lessthan 1000 g/mol). Preferred cyclic dienes include cyclopentadiene,vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene,dicyclopentadiene or higher ring containing diolefins with or withoutsubstituents at various ring positions. Preferred dienes include bothcis and trans 1,4-hexadiene.

Non-limiting examples of preferred polar unsaturated monomers useful inthis invention include nitro substituted monomers including6-nitro-1-hexene; amine substituted monomers includingN-methylallylamine, N-allylcyclopentylamine, and N-allyl-hexylamine;ketone substituted monomers including methyl vinyl ketone, ethyl vinylketone, and 5-hexen 2-one; aldehyde substituted monomers includingacrolein, 2,2-dimethyl-4-pentenal, undecylenic aldehyde, and2,4-dimethyl-2,6-heptadienal; alcohol substituted monomers includingallyl alcohol, 7-octen-1-ol, 7-octene-1,2-diol, 10-undecen-1-ol,10-undecene-1,2-diol, 2-methyl-3-buten-1-ol; acetal, epoxide and orether substituted monomers including4-hex-5-enyl-2,2-dimethyl-[1,3]dioxolane,2,2-dimethyl-4-non-8-enyl-[1,3]dioxolane, acrolein dimethyl acetal,butadiene monoxide, 1,2-epoxy-7-octene, 1,2-epoxy-9-decene,1,2-epoxy-5-hexene, 2-methyl-2-vinyloxirane, allyl glycidyl ether,2,5-dihydrofuran, 2-cyclopenten-1-one ethylene ketal,11-methoxyundec-1-ene, and 8-methoxyoct-1-ene; sulfur containingmonomers including allyl disulfide; acid and ester substituted monomersincluding acrylic acid, vinylacetic acid, 4-pentenoic acid,2,2-dimethyl-4-pentenoic acid, 6-heptenoic acid, trans-2,4-pentadienoicacid, 2,6-heptadienoic acid, methyl acrylate, ethyl acrylate, tert-butylacrylate, n-butyl acrylate, methacrylic acid, methyl methacrylate, ethylmethacrylate, tert-butyl methacrylate, n-butyl methacrylate,hydroxypropyl acrylate, acetic acid oct-7-enyl ester, non-8-enoic acidmethyl ester, acetic acid undec-10-enyl ester, dodec-11-enoic acidmethyl ester, propionic acid undec-10-enyl ester, dodec-11-enoic acidethyl ester, and nonylphenoxypolyetheroxy acrylate; siloxy containingmonomers including trimethyloct-7-enyloxy silane, andtrimethylundec-10-enyloxy silane, polar functionalized norbornenemonomers including 5-norbornene-2-carbonitrile,5-norbornene-2-carboxaldehyde, 5-norbornene-2-carboxylic acid,cis-5-norbornene-endo-2,3-dicarboxylic acid,5-norbornene-2,2,-dimethanol, cis-5-norbornene-endo-2,3-dicarboxylicanhydride, 5-norbornene-2-endo-3-endo-dimethanol,5-norbornene-2-endo-3-exo-dimethanol, 5-norbornene-2-methanol,5-norbornene-2-ol, 5-norbornene-2-yl acetate,1-[2-(5-norbornene-2-yl)ethyl]-3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane,2-benzoyl-5-norbornene, 2-acetyl-5-norbornene, 7-synmethoxymethyl-5-norbornen-2-one, 5-norbornen-2-ol, and5-norbornen-2-yloxy-trimethylsilane, and partially fluorinated monomersincluding nonafluoro-1-hexene, allyl-1,1,2,2,-tetrafluoroethyl ether,2,2,3,3-tetrafluoro-non-8-enoic acid ethyl ester,1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoro-oct-7-enyloxy)-ethanesulfonylfluoride, acrylic acid2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-octyl ester, and1,1,2,2-tetrafluoro-2-(1,1,2,2,3,3,4,4-octafluoro-dec-9-enyloxy)-ethanesulfonylfluoride.

In an embodiment herein, the process described herein is used to producean oligomer of any of the monomers listed above. Preferred oligomersinclude oligomers of any C₂ to C₂₀ olefins, preferably C₂ to C₁₂alpha-olefins, most preferably oligomers comprising ethylene, propyleneand or butene are prepared. A preferred feedstock for theoligomerization process is the alpha-olefin, ethylene. But otheralpha-olefins, including but not limited to propylene and 1-butene, mayalso be used alone or combined with ethylene. Preferred alpha-olefinsinclude any C₂ to C₄₀ alpha-olefin, preferably and C₂ to C₂₀alpha-olefin, preferably any C₂ to C₁₂ alpha-olefin, preferablyethylene, propylene, and butene, most preferably ethylene.

Dienes may be used in the processes described herein, preferablyalpha-omega-dienes are used alone or in combination with mono-alphaolefins.

In a preferred embodiment the process described herein may be used toproduce homopolymers or copolymers. (For the purposes of this inventionand the claims thereto a copolymer may comprise two, three, four or moredifferent monomer units.) Preferred polymers produced herein includehomopolymers or copolymers of any of the above monomers. In a preferredembodiment the polymer is a homopolymer of any C₂ to C₁₂ alpha-olefin.Preferably the polymer is a homopolymer of ethylene or a homopolymer ofpropylene. In another embodiment the polymer is a copolymer comprisingethylene and one or more of any of the monomers listed above. In anotherembodiment the polymer is a copolymer comprising propylene and one ormore of any of the monomers listed above. In another preferredembodiment the homopolymers or copolymers described, additionallycomprise one or more diolefin comonomers, preferably one or more C₄ toC₄₀ diolefins.

In another preferred embodiment the polymer produced herein is acopolymer of ethylene and one or more C₃ to C₂₀ linear, branched orcyclic monomers, preferably one or more C₃ to C₁₂ linear, branched orcyclic alpha-olefins. Preferably the polymer produced herein is acopolymer of ethylene and one or more of propylene, butene, pentene,hexene, heptene, octene, nonene, decene, dodecene,4-methylpentene-1,3-methylpentene-1, 3,5,5-trimethylhexene-1,cyclopentene, 4-methylcyclopentene, cyclohexene, and4-methylcyclohexene.

In another preferred embodiment the polymer produced herein is acopolymer of propylene and one or more C₂ or C₄ to C₂₀ linear, branchedor cyclic monomers, preferably one or more C₂ or C₄ to C₁₂ linear,branched or cyclic alpha-olefins. Preferably the polymer produced hereinis a copolymer of propylene and one or more of ethylene, butene,pentene, hexene, heptene, octene, nonene, decene, dodecene,4-methylpentene-1,3-methylpentene-1, and 3,5,5-trimethylhexene-1.

In a preferred embodiment, the polymer produced herein is a homopolymerof norbornene or a copolymer of norbornene and a substituted norbornene,including polar functionalized norbornenes.

In a preferred embodiment the polymers described above further compriseone or more dienes at up to 10 weight %, preferably at 0.00001 to 1.0weight %, preferably 0.002 to 0.5 weight %, even more preferably 0.003to 0.2 weight %, based upon the total weight of the composition. In someembodiments 500 ppm or less of diene is added to the polymerization,preferably 400 ppm or less, preferably or 300 ppm or less. In otherembodiments at least 50 ppm of diene is added to the polymerization, or100 ppm or more, or 150 ppm or more.

In a preferred embodiment the copolymers described herein comprise atleast 50 mole % of a first monomer and up to 50 mole % of othermonomers.

In another embodiment, the polymer comprises:

-   a first monomer present at from 40 to 95 mole %, preferably 50 to 90    mole %, preferably 60 to 80 mole %, and-   a comonomer present at from 5 to 60 mole %, preferably 10 to 40 mole    %, more preferably 20 to 40 mole %, and-   a termonomer present at from 0 to 10 mole %, more preferably from    0.5 to 5 mole %, more preferably 1 to 3 mole %.

In a preferred embodiment the first monomer comprises one or more of anyC₃ to C₈ linear branched or cyclic alpha-olefins, including propylene,butene, (and all isomers thereof), pentene (and all isomers thereof),hexene (and all isomers thereof), heptene (and all isomers thereof), andoctene (and all isomers thereof). Preferred monomers include propylene,1-butene, 1-hexene, 1-octene, cyclopentene, cyclohexene, cyclooctene,hexadiene, cyclohexadiene and the like.

In a preferred embodiment the comonomer comprises one or more of any C₂to C₄₀ linear, branched or cyclic alpha-olefins (provided ethylene, ifpresent, is present at 5 mole % or less), including ethylene, propylene,butene, pentene, hexene, heptene, and octene, nonene, decene, undecene,dodecene, hexadecene, butadiene, hexadiene, heptadiene, pentadiene,octadiene, nonadiene, decadiene, dodecadiene,3,5,5-trimethylhexene-1,3-methylpentene-1,4-methylpentene-1,cyclopentadiene, and cyclohexene.

In a preferred embodiment the termonomer comprises one or more of any C₂to C₄₀ linear, branched or cyclic alpha-olefins, (provided ethylene, ifpresent, is present at 5 mole % or less), including ethylene, propylene,butene, pentene, hexene, heptene, and octene, nonene, decene, undecene,dodecene, hexadecene, butadiene, hexadiene, heptadiene, pentadiene,octadiene, nonadiene, decadiene, dodecadiene,3,5,5-trimethylhexene-1,3-methylpentene-1,4-methylpentene-1,cyclopentadiene, and cyclohexene.

Polymer Produced

The polymers produced by the process of the invention can be used in awide variety of products and end-use applications. Preferred polymersproduced herein may have an M_(n) (number-average molecular weight)value from 300 to 1,000,000, or between from 700 to 300,000. For lowweight molecular weight applications, such as those copolymers useful inlubricating and fuel oil compositions, an M_(n) of 300 to 20,000 iscontemplated, or less than or equal to 10,000. Additionally, preferredpolymers and copolymers produced herein may have a molecular weightdistribution (MWD) in the range of ≧1, or ≧1.5 or ≦8, or ≦6 or ≦4.

The polymers produced are preferably homo- and co-polymers of ethyleneand or propylene and include linear low density polyethylene,elastomers, plastomers, high-density polyethylenes, medium densitypolyethylenes, low density polyethylenes, polypropylene andpolypropylene copolymers. Polymers, typically ethylene based copolymers,have a density of from 0.80 g/cc to 0.97 g/cc, preferably from 0.86 g/ccto 0.97 g/cc; density being measured in accordance with ASTM-D-1238.

The polymers of this invention may be blended and/or coextruded with anyother polymer. Non-limiting examples of other polymers include linearlow density polyethylenes, elastomers, plastomers, high pressure lowdensity polyethylene, high density polyethylenes, isotacticpolypropylene, ethylene propylene copolymers and the like.

Polymers produced by the process of the invention and blends thereof areuseful in such forming operations as film, sheet, and fiber extrusionand co-extrusion as well as blow molding, injection molding,roto-molding. Films include blown or cast films formed by coextrusion orby lamination useful as shrink film, cling film, stretch film, sealingfilm, oriented films, and the like.

EXAMPLES

Examples S1 and S2 were produced in a 0.5-liter autoclave reactorequipped with a stirrer, an external water/steam jacket for temperaturecontrol, a regulated supply of dry nitrogen, ethylene, propylene, and aseptum inlet for introduction of other solvents, catalysts and scavengersolutions. The polymerizations were conducted in a semi-batch mode withcontinuous ethylene feed. The reactor was dried and degassed thoroughlyprior to use. All the solvents and monomers were purified by passingthrough a 1-liter basic alumina column activated at 600° C., followed bya column of molecular sieves activated at 600° C. or Selexsorb CD columnprior to transferring into the reactor. For the runs with metallocenecatalysts, 0.5 ml of triisobutyl aluminum (25 wt. % in toluene) wasfirst injected into the reactor, then propylene and solvent includingfluorocarbon were added into the reactor. The mixture was stirred andheated to a desired reaction temperature, followed by the addition ofethylene. The ethylene was fed on demand to maintain a relative constantreactor pressure during the polymerization reaction. The ethyleneconsumption was monitored during the reaction using a mass flow meter.The amount of ethylene addition was controlled by setting the ethylenefeed pressure and was reported as a differential pressure in excess ofthe combined vapor pressure of monomers and solvents prior to ethyleneaddition. Catalyst solution was injected into the reactor when thesystem reach the desired temperature and pressure after introducingethylene. The polymerization was terminated based on the total ethyleneconsumption. Thereafter, the reactor was cooled down and unreactedpropylene and solvent were vented to the atmosphere. The resultingmixture, containing mostly solvent, fluorocarbon, polymer and unreactedmonomers, was collected in a collection box and first air-dried in ahood to evaporate most of the solvent, and then dried in a vacuum ovenat a temperature of about 90° C. for about 12 hours.

Rac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl(Catalyst B) was used. The catalyst was preactivated withN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (all thecatalyst and activator were obtained from Albemarle) at a molar ratio of1:1 to 1:1.1. Stock solutions of catalyst and activator were firstprepared. Then all the appropriate components were transferred into acatalyst charge tube using syringes. All of these manipulations werecarried out in a drybox. The activated catalyst solution in the chargetube was flushed into the reactor using about 5 ml of toluene. HFC-245fais 1,1,1,3,3-pentafluoropropane obtained from Honeywell under the tradename Enovate 3000. The detailed conditions are listed in Table E1.Examples S1 was a comparative example. The polymer produced in S1 was insolution at the end of reaction. Polymer produced in S2 was insuspension state at the end of reaction.

TABLE E1 Polymerization conditions for examples S1 and S2 Run # S1Comparative S2 Reaction Temperature (° C.) 70 70 Catalyst Catalyst BCatalyst B Catalyst feed (mg) 1 1 Solvent Hexane HFC245fa Solvent (ml)125 125 Propylene (ml) 125 125 Ethylene (psi//MPa) 70//0.48 70//0.48Reaction time (min) 6 7 Yield (g) 48.6 34.4 Ethylene content (%) 17.021.2 Tc (° C.) 45.5 20 Tm (° C.) 94.6 61.8 Tg (° C.) −−32.7 −33.5 Heatof fusion (J/g) 3.0 3 Crystallinity (%) 1.6 1.6

The polymerizations for Examples S3 to S6 were carried in a liquidfilled, single-stage continuous reactor. The reactor was a 0.5-literstainless steel autoclave reactor and was equipped with a stirrer, awater-cooling/steam-heating element with a temperature controller, and apressure controller. Solvents, monomers such as ethylene and propylene,and comonomers (such as butene and hexene), if present, were firstpurified by passing through a three-column purification system. Thepurification system consists of an Oxiclear column (Model # RGP-R1-500from Labclear) followed by a 5 A and a 3 A molecular sieve columns.Purification columns were regenerated periodically whenever there isevidence of lower activity of polymerization. Both the 3 A and 5 Amolecular sieve columns were regenerated in-house under nitrogen at aset temperature of 260° C. and 315° C., respectively. The molecularsieve material was purchased from Aldrich. The Oxiclear column was usedas received.

The solvent, monomers and comonomers were fed into a manifold first.Ethylene from in-house supply was delivered as a gas solubilized in thechilled solvent/monomer mixture in the manifold. The mixture of solventand monomers were then chilled to about −15° C. by passing through achiller before fed into the reactor through a single tube. All liquidflow rates were measured using Brooks mass flow meters or Micro-MotionCoriolis-type flow meters. Ethylene flow rate was metered through aBrooks mass flow controller.

The catalyst compounds used were rac-dimethylsilylbisindenyl hafniumdimethyl (Catalyst A), and dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl (Catalyst C) (Both were obtainedfrom Albemarle). The catalysts were preactivated withN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (obtained fromAlbemarle) at a molar ratio of 1:1 to 1:1.1 in 700 ml of toluene for atleast 10 minutes prior to the polymerization reaction. The catalystsystems were diluted to a concentration of catalyst ranging from 0.2 to1.4 mg/ml in toluene. All catalyst solutions were kept in an inertatmosphere with <1.5 ppm water content and fed into reactor by meteringpumps. The contact of catalyst, solvent fluorocarbon and monomers tookplace in the reactor. Catalyst pumps were calibrated periodically usingtoluene as the calibrating medium. Catalyst concentration in the feedwas controlled through changing the catalyst concentration in catalystsolution and/or changing in the feed rate of catalyst solution. The feedrate of catalyst solution varied in a range of 0.2 to 5 ml/minute.

As an impurity scavenger, 250 ml of tri-n-octylaluminum (TNOA) (25 wt. %in toluene, Akzo Noble) was diluted in 22.83 kilogram of hexane. Thediluted TNOA solution was stored in a 37.9-liter cylinder under nitrogenblanket. The solution was used for all polymerization runs until about90% of consumption, and then a new batch was prepared. Feed rates of thetri-n-octylaluminum (TNOA) solution varied from polymerization reactionto reaction, ranging from 0 (no scavenger) to 4 ml per minute.

The reactor was first cleaned by continuously pumping solvent (e.g.,hexane) and scavenger through the reactor system for at least one hourat a maximum allowed temperature (about 150° C.). After cleaning, thereactor was heated/cooled to the desired temperature using water/steammixture flowing through the reactor jacket and controlled at a setpressure with controlled solvent flow. Monomers and catalyst solutionswere then fed into the reactor. An automatic temperature control systemwas used to control and maintain the reactor at a set temperature. Onsetof polymerization activity was determined by observations of a viscousproduct and lower temperature of water-steam mixture. Once the activitywas established and system reached steady state, the reactor was linedout by continuing operating the system under the established conditionfor a time period of at least five times of mean residence time prior tosample collection. The resulting mixture, containing mostly solvent,polymer and unreacted monomers, was collected in a collection box. Thecollected samples were first air-dried in a hood to evaporate most ofthe solvent, and then dried in a vacuum oven at a temperature of about90° C. for about 12 hours. The vacuum oven dried samples were weighed toobtain yields. All the reactions were carried out at a pressure of 2.41MPa-g.

TABLE E2 Polymerization conditions for examples S3 to S6 Run # S3 S4 S5S6 Reaction temperature 80 80 80 80 (° C.) Propylene feed (g/min) 14 1414 14 Ethylene feed (SLPM) 0.8 1.6 2 2 Hexane feed (ml/min) 60 60 40 40HFC245fa feed (ml/min) 20 20 20 15 Catalyst Catalyst A Catalyst ACatalyst C Catalyst C Catalyst feed (mol/min) 8.99E−07 8.99E−07 2.23E−074.19E−08 Yield (gram/min) 12.1 12.9 7.4 4.3 Conversion (%) 81.1 81.845.6 26.4 Tc (° C.) 20.3 Tm (° C.) 59.1 Tg (° C.) −25.5 −29.9 −24.6−28.9 Heat of fusion (J/g) 8.7 0 0 0 Ethylene content (wt %) 10.7 17.718.0 20.2 Mn (g/mol) 28,900 28,700 189,300 55,800 Mw (g/mol) 66,40064,900 504,400 163,500 Mz(g/mol) 118,000 115,500 970,100 346,300 Mw/Mn2.3 2.3 2.7 2.9Tests and Materials.

Molecular weight (Mw, Mn, and Mz) and molecular weight distribution(Mw/Mn) of the polymers, if reported, were determined using gelpermeation chromatography (GPC) on a Water 150 C high temperaturechromatographic unit equipped with a DRI detector and four linear mixedbed columns (Polymer Laboratories PLgel Mixed-B LS, 20-micron particlesize). The oven temperature was at 160° C. with the autosampler hot zoneat 160° C. and the warm zone at 145° C. About 0.2 wt. % of polymersample was dissolved in 1,2,4-trichlorobenzene containing 200 ppm2,6-di-t-butyl-4-methylphenol. The flow rate was 1.0 milliliter/minuteand the injection size is 100 microliters.

Peak melting point (Tm) and peak crystallization temperature (Tc) weredetermined using the following procedure according to ASTM E 794-85.Differential scanning calorimetric (DSC) data was obtained using a TAInstruments model 2910 machine. Samples weighing approximately 7-10 mgwere sealed in aluminum sample pans. The DSC data was recorded by firstcooling the sample to −100° C. and then gradually heating it to 200° C.at a rate of 10° C./minute. The sample was kept at 200° C. for 5 minutesbefore a second cooling-heating cycle was applied. Both the first andsecond cycle thermal events were recorded. Areas under the meltingcurves were measured and used to determine the heat of fusion and thedegree of crystallinity according to ASTM 3417-99. The percentcrystallinity was calculated using the formula, [area under the curve(Joules/gram)/B(Joules/gram)]*100, where B is the heat of fusion for thehomopolymer of the major monomer component. These values for B are to beobtained from the Polymer Handbook, Fourth Edition, published by JohnWiley and Sons, New York 1999). A value of 189 J/g (B) was used as theheat of fusion for 100% crystalline polypropylene.

The glass transition temperature (Tg) was measured by ASTM E 1356 usinga TA Instruments model 2910 machine.

Ethylene content for samples produced using fluorocarbon was determinedusing ¹³C nuclear magnetic resonance (NMR). All the peaks in the NMRspectra are referenced by setting the mmmm methyl peak to 21.8 ppm. Allsecondary carbons are defined by the peak regions in Table A. Naming ofthe peaks was made in accordance with a method by Carman, et al. inRubber Chemistry and Technology, 44 (1971), page 781, where e.g., S_(αδ)denotes a peak area of the αδ⁺ secondary carbon peak.

TABLE A ppm range Assignment 45-48 S_(αα) 36-39 S_(αδ) + S_(αγ) 34-36S_(αβ) 30.7 S_(γγ) 30.3 S_(γδ) 29.9 S_(δδ) 27.5-27.7 S_(βγ) 27.1-27.3S_(βδ) 24.5-25   S_(ββ)All tertiary carbons are defined by the peak regions in Table B (Notethat the peak region of 30.7-31 ppm has overlapping peaks of secondaryand tertiary carbons):

TABLE B ppm range Assignment 33.6-34   T_(γγ) 33.4-33.6 T_(γδ) 33.2T_(δδ)   31-31.4 T_(βγ) 30.7-31   (T_(βδ) + S_(γγ)) 28-29 T_(ββ)The T_(βδ) and S_(γγ) peaks are overlapping. The area of S_(γγ) peak canbe calculated as:S _(γγ)=(S _(βδ) −S _(γδ))/2  (A)

-   In Table A, the area of S_(γγ) peak was calculated by equation A,    rather than by direct integration. Total area of secondary    carbons (S) was calculated by the sum of all areas in Table A. Total    area of tertiary carbons (T) was calculated by the sum of all areas    in Table B subtracted by the area of S_(γγ) peak, as calculated by    equation (A).-   Total area of primary carbons (P) is the total area between 19 and    23 ppm.-   Ethylene content was calculated by    E wt %=(S−T/2−P/2)/(S+T+P)  (B)

The ethylene content of ethylene/propylene copolymers produced usinghydrocarbon solvent was determined using FTIR according to the followingtechnique. A thin homogeneous film of polymer, pressed at a temperatureof about 150° C., was mounted on a Perkin Elmer Spectrum 2000 infraredspectrophotometer. A full spectrum of the sample from 600 cm⁻¹ to 4000cm⁻¹ was recorded and the ethylene content in wt. % was calculatedaccording to the following equation:ethylene content(wt. %)=72.698−86.495X+13.696X ²where X=AR/(AR+1). The area under propylene band at ˜1165 cm⁻¹ and thearea of ethylene band at ˜732 cm⁻¹ in the spectrum were calculated. Thebaseline integration range for the methylene rocking band is nominallyfrom 695 cm⁻¹ to the minimum between 745 and 775 cm⁻¹. For thepolypropylene band the baseline and integration range is nominally from1195 to 1126 cm⁻¹. AR is the ratio of the area for the peak at ˜1165cm⁻¹ to the area of the peak at ˜732 cm⁻¹.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures. As isapparent from the foregoing general description and the specificembodiments, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. Accordingly, it is not intended thatthe invention be limited thereby. Likewise, the term “comprising” isconsidered synonymous with the term “including” for purposes ofAustralian law.

1. A process to produce polyolefins comprising contacting a catalyst or catalyst system with olefin(s) in the presence of a fluorinated hydrocarbon at a polymerization temperature above the onset melting point of the wet polymer, wherein the fluorinated hydrocarbon is present at 5 to 99 volume %, based upon the total volume of fluorocarbons, any hydrocarbon solvents present and any unreacted monomer; provided that if the wet polymer does not have an onset melting point, then the polymerization temperature is 70° C. or more and wherein the wet polymer is polymer that has been contacted for at least 12 hours at 50° C. in a sealed chamber with the same fluorocarbon(s) and or hydrocarbons(s) used in the polymerization process medium present in the same proportions.
 2. A solution process to produce polyolefins comprising contacting a catalyst or catalyst system with olefin(s) in the presence of a fluorinated hydrocarbon at a polymerization temperature above the melting point of the wet polymer, wherein the fluorinated hydrocarbon is present at 5 volume % or more, based upon the total volume of fluorocarbons and any hydrocarbon solvents present and wherein the wet polymer is polymer that has been contacted for at least 12 hours at 50° C. in a sealed chamber with the same fluorocarbon(s) and or hydrocarbons(s) used in the polymerization process medium present in the same proportions.
 3. The process of claim 1 wherein the polymerization temperature is above 100° C.
 4. The process of claim 1 wherein the polymerization temperature is above 120° C.
 5. The process of claim 1 wherein the polymerization temperature is between 100 and 250° C.
 6. The process of claim 1 wherein the polymerization effluent comprises a hydrocarbon solvent or diluent.
 7. The process of claim 6 wherein the hydrocarbon solvent or diluent is selected from the group consisting of propane, n-butane, isobutane, n-pentane, isopentane, cyclopentane, neopentane, n-hexane, isohexane, octane, isooctane, and cyclohexane.
 8. The process of claim 1 where the fluorinated hydrocarbon is present at 10 to 90 volume %, based upon the volume of the polymerization medium.
 9. The process of claim 1 wherein the fluorinated hydrocarbon comprises a perfluorinated hydrocarbon.
 10. The process of claim 1 wherein the fluorinated hydrocarbon comprises a hydrofluorocarbon.
 11. The process of claim 1 wherein the fluorinated hydrocarbon is represented by the formula: C_(x)H_(y)F_(z) wherein x is an integer from 1 to 40, y is an integer greater than or equal to 0 and z is an integer and is at least one.
 12. The process of claim 1 wherein the fluorinated hydrocarbon is selected from the group consisting of fluoromethane; difluoromethane; trifluoromethane; fluoroethane; 1,1-difluoroethane; 1,2-difluoroethane; 1,1,1-trifluoroethane; 1,1,2-trifluoroethane; 1,1,1,2-tetrafluoroethane; 1,1,2,2-tetrafluoroethane; 1,1,1,2,2-pentafluoroethane; 1-fluoropropane; 2-fluoropropane; 1,1-difluoropropane; 1,2-difluoropropane; 1,3-difluoropropane; 2,2-difluoropropane; 1,1,1-trifluoropropane; 1,1,2-trifluoropropane; 1,1,3-trifluoropropane; 1,2,2-trifluoropropane; 1,2,3-trifluoropropane; 1,1,1,2-tetrafluoropropane; 1,1,1,3-tetrafluoropropane; 1,1,2,2-tetrafluoropropane; 1,1,2,3-tetrafluoropropane; 1,1,3,3-tetrafluoropropane; 1,2,2,3-tetrafluoropropane; 1,1,1,2,2-pentafluoropropane; 1,1,1,2,3-pentafluoropropane; 1,1,1,3,3-pentafluoropropane; 1,1,2,2,3-pentafluoropropane; 1,1,2,3,3-pentafluoropropane; 1,1,1,2,2,3-hexafluoropropane; 1,1,1,2,3,3-hexafluoropropane; 1,1,1,3,3,3-hexafluoropropane; 1,1,1,2,2,3,3-heptafluoropropane; 1,1,1,2,3,3,3-heptafluoropropane; 1-fluorobutane; 2-fluorobutane; 1,1-difluorobutane; 1,2-difluorobutane; 1,3-difluorobutane; 1,4-difluorobutane; 2,2-difluorobutane; 2,3-difluorobutane; 1,1,1-trifluorobutane; 1,1,2-trifluorobutane; 1,1,3-trifluorobutane; 1,1,4-trifluorobutane; 1,2,2-trifluorobutane; 1,2,3-trifluorobutane; 1,3,3-trifluorobutane; 2,2,3-trifluorobutane; 1,1,1,2-tetrafluorobutane; 1,1,1,3-tetrafluorobutane; 1,1,1,4-tetrafluorobutane; 1,1,2,2-tetrafluorobutane; 1,1,2,3-tetrafluorobutane; 1,1,2,4-tetrafluorobutane; 1,1,3,3-tetrafluorobutane; 1,1,3,4-tetrafluorobutane; 1,1,4,4-tetrafluorobutane; 1,2,2,3-tetrafluorobutane; 1,2,2,4-tetrafluorobutane; 1,2,3,3-tetrafluorobutane; 1,2,3,4-tetrafluorobutane; 2,2,3,3-tetrafluorobutane; 1,1,1,2,2-pentafluorobutane; 1,1,1,2,3-pentafluorobutane; 1,1,1,2,4-pentafluorobutane; 1,1,1,3,3-pentafluorobutane; 1,1,1,3,4-pentafluorobutane; 1,1,1,4,4-pentafluorobutane; 1,1,2,2,3-pentafluorobutane; 1,1,2,2,4-pentafluorobutane; 1,1,2,3,3-pentafluorobutane; 1,1,2,4,4-pentafluorobutane; 1,1,3,3,4-pentafluorobutane; 1,2,2,3,3-pentafluorobutane; 1,2,2,3,4-pentafluorobutane; 1,1,1,2,2,3-hexafluorobutane; 1,1,1,2,2,4-hexafluorobutane; 1,1,1,2,3,3-hexafluorobutane, 1,1,1,2,3,4-hexafluorobutane; 1,1,1,2,4,4-hexafluorobutane; 1,1,1,3,3,4-hexafluorobutane; 1,1,1,3,4,4-hexafluorobutane; 1,1,1,4,4,4-hexafluorobutane; 1,1,2,2,3,3-hexafluorobutane; 1,1,2,2,3,4-hexafluorobutane; 1,1,2,2,4,4-hexafluorobutane; 1,1,2,3,3,4-hexafluorobutane; 1,1,2,3,4,4-hexafluorobutane; 1,2,2,3,3,4-hexafluorobutane; 1,1,1,2,2,3,3-heptafluorobutane; 1,1,1,2,2,4,4-heptafluorobutane; 1,1,1,2,2,3,4-heptafluorobutane; 1,1,1,2,3,3,4-heptafluorobutane; 1,1,1,2,3,4,4-heptafluorobutane; 1,1,1,2,4,4,4-heptafluorobutane; 1,1,1,3,3,4,4-heptafluorobutane; 1,1,1,2,2,3,3,4-octafluorobutane; 1,1,1,2,2,3,4,4-octafluorobutane; 1,1,1,2,3,3,4,4-octafluorobutane; 1,1,1,2,2,4,4,4-octafluorobutane; 1,1,1,2,3,4,4,4-octafluorobutane; 1,1,1,2,2,3,3,4,4-nonafluorobutane; 1,1,1,2,2,3,4,4,4-nonafluorobutane; 1-fluoro-2-methylpropane; 1,1-difluoro-2-methylpropane; 1,3-difluoro-2-methylpropane; 1,1,1-trifluoro-2-methylpropane; 1,1,3-trifluoro-2-methylpropane; 1,3-difluoro-2-(fluoromethyl)propane; 1,1,1,3-tetrafluoro-2-methylpropane; 1,1,3,3-tetrafluoro-2-methylpropane; 1,1,3-trifluoro-2-(fluoromethyl)propane; 1,1,1,3,3-pentafluoro-2-methylpropane; 1,1,3,3-tetrafluoro-2-(fluoromethyl)propane; 1,1,1,3-tetrafluoro-2-(fluoromethyl)propane; fluorocyclobutane; 1,1-difluorocyclobutane; 1,2-difluorocyclobutane; 1,3-difluorocyclobutane; 1,1,2-trifluorocyclobutane; 1,1,3-trifluorocyclobutane; 1,2,3-trifluorocyclobutane; 1,1,2,2-tetrafluorocyclobutane; 1,1,3,3-tetrafluorocyclobutane; 1,1,2,2,3-pentafluorocyclobutane; 1,1,2,3,3-pentafluorocyclobutane; 1,1,2,2,3,3-hexafluorocyclobutane; 1,1,2,2,3,4-hexafluorocyclobutane; 1,1,2,3,3,4-hexafluorocyclobutane; and 1,1,2,2,3,3,4-heptafluorocyclobutane.
 13. The process of claim 1 wherein the fluorinated hydrocarbon is selected from the group consisting of difluoromethane, trifluoromethane, 1,1-difluoroethane, 1,1,1-trifluoroethane, fluoromethane, and 1,1,1,2-tetrafluoroethane.
 14. The process of claim 1 wherein the fluorinated hydrocarbon is selected from the group consisting of 1,1,1,3,3,3-hexafluoropropane, 1,1,1,2-tetrafluoroethane, 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-pentafluorobutane, octafluorocyclobutane, and 2,3-dihydrodecafluoropentane.
 15. The process of claim 1 wherein the polymerization medium comprises ethylene.
 16. The process of claim 1 where the polymerization medium comprises propylene.
 17. The process of claim 1 where the fluorinated hydrocarbon is not a perfluorinated C4 to C10 alkane.
 18. The process of claim 1 wherein the polymerization further comprises a hydrocarbon and the fluorinated hydrocarbon is soluble in the hydrocarbon.
 19. The process of claim 1 where the fluorinated hydrocarbon is present at 20 to 90 volume %, based upon the volume of the polymerization medium.
 20. The process of claim 1 wherein the fluorinated hydrocarbon is present at least 1 weight % based upon the weight of the fluorinated hydrocarbon and any hydrocarbon solvent or diluent present, and where the process further comprises recovering a polymer having an Mw of 70,000 or more and a percent crystallinity of 20% or more.
 21. The process of claim 1 further comprising introducing a fluorinated hydrocarbon into the polymer effluent.
 22. The process of claim 11 wherein z is 2 or more.
 23. The process of claim 1 wherein the process is a continuous process.
 24. The process of claim 1 wherein the olefins are aliphatic or alicyclic hydrocarbons.
 25. The process of claim 1 wherein the olefins are linear or branched alpha-olefins.
 26. The process of claim 1 wherein the olefins are C2 to C40 linear or branched alpha-olefins.
 27. The process of claim 1 wherein the olefins are selected from the group consisting of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, and dodecene.
 28. The process of claim 1 wherein the fluorocarbon consists essentially of hydrofluorocarbons.
 29. The process of claim 1 where the polymer produced has a crystallinity of less than 20%.
 30. The process of claim 2 wherein the polymerization temperature is above 100° C.
 31. The process of claim 2 wherein the polymerization temperature is above 120° C.
 32. The process of claim 2 wherein the polymerization temperature is between 100 and 250° C.
 33. The process of claim 2 wherein the polymerization effluent comprises a hydrocarbon solvent or diluent.
 34. The process of claim 33 wherein the hydrocarbon solvent or diluent is selected from the group consisting of propane, n-butane, isobutane, n-pentane, isopentane, cyclopentane, neopentane, n-hexane, isohexane, octane, isooctane, and cyclohexane.
 35. The process of claim 2 where the fluorinated hydrocarbon is present at 5 to 99 volume %, based upon the volume of the polymerization medium.
 36. The process of claim 2 wherein the fluorinated hydrocarbon comprises a perfluorinated hydrocarbon.
 37. The process of claim 2 wherein the fluorinated hydrocarbon comprises a hydrofluorocarbon.
 38. The process of claim 2 wherein the fluorinated hydrocarbon is represented by the formula: C_(x)H_(y)F_(z) wherein x is an integer from 1 to 40, y is an integer greater than or equal to 0 and z is an integer and is at least one.
 39. The process of claim 2 wherein the fluorinated hydrocarbon is selected from the group consisting of fluoromethane; difluoromethane; trifluoromethane; fluoroethane; 1,1-difluoroethane; 1,2-difluoroethane; 1,1,1-trifluoroethane; 1,1,2-trifluoroethane; 1,1,1,2-tetrafluoroethane; 1,1,2,2-tetrafluoroethane; 1,1,1,2,2-pentafluoroethane; 1-fluoropropane; 2-fluoropropane; 1,1-difluoropropane; 1,2-difluoropropane; 1,3-difluoropropane; 2,2-difluoropropane; 1,1,1-trifluoropropane; 1,1,2-trifluoropropane; 1,1,3-trifluoropropane; 1,2,2-trifluoropropane; 1,2,3-trifluoropropane; 1,1,1,2-tetrafluoropropane; 1,1,1,3-tetrafluoropropane; 1,1,2,2-tetrafluoropropane; 1,1,2,3-tetrafluoropropane; 1,1,3,3-tetrafluoropropane; 1,2,2,3-tetrafluoropropane; 1,1,1,2,2-pentafluoropropane; 1,1,1,2,3-pentafluoropropane; 1,1,1,3,3-pentafluoropropane; 1,1,2,2,3-pentafluoropropane; 1,1,2,3,3-pentafluoropropane; 1,1,1,2,2,3-hexafluoropropane; 1,1,1,2,3,3-hexafluoropropane; 1,1,1,3,3,3-hexafluoropropane; 1,1,1,2,2,3,3-heptafluoropropane; 1,1,1,2,3,3,3-heptafluoropropane; 1-fluorobutane; 2-fluorobutane; 1,1-difluorobutane; 1,2-difluorobutane; 1,3-difluorobutane; 1,4-difluorobutane; 2,2-difluorobutane; 2,3-difluorobutane; 1,1,1-trifluorobutane; 1,1,2-trifluorobutane; 1,1,3-trifluorobutane; 1,1,4-trifluorobutane; 1,2,2-trifluorobutane; 1,2,3-trifluorobutane; 1,3,3-trifluorobutane; 2,2,3-trifluorobutane; 1,1,1,2-tetrafluorobutane; 1,1,1,3-tetrafluorobutane; 1,1,1,4-tetrafluorobutane; 1,1,2,2-tetrafluorobutane; 1,1,2,3-tetrafluorobutane; 1,1,2,4-tetrafluorobutane; 1,1,3,3-tetrafluorobutane; 1,1,3,4-tetrafluorobutane; 1,1,4,4-tetrafluorobutane; 1,2,2,3-tetrafluorobutane; 1,2,2,4-tetrafluorobutane; 1,2,3,3-tetrafluorobutane; 1,2,3,4-tetrafluorobutane; 2,2,3,3-tetrafluorobutane; 1,1,1,2,2-pentafluorobutane; ,1,1,1,2,3-pentafluorobutane; 1,1,1,2,4-pentafluorobutane; 1,1,1,3,3-pentafluorobutane; 1,1,1,3,4-pentafluorobutane; 1,1,1,4,4-pentafluorobutane; 1,1,2,2,3-pentafluorobutane; 1,1,2,2,4-pentafluorobutane; 1,1,2,3,3-pentafluorobutane; 1,1,2,4,4-pentafluorobutane; 1,1,3,3,4-pentafluorobutane; 1,2,2,3,3-pentafluorobutane; 1,2,2,3,4-pentafluorobutane; 1,1,1,2,2,3-hexafluorobutane; 1,1,1,2,2,4-hexafluorobutane; 1,1,1,2,3,3-hexafluorobutane, 1,1,1,2,3,4-hexafluorobutane; 1,1,1,2,4,4-hexafluorobutane; 1,1,1,3,3,4-hexafluorobutane; 1,1,1,3,4,4-hexafluorobutane; 1,1,1,4,4,4-hexafluorobutane; 1,1,2,2,3,3-hexafluorobutane; 1,1,2,2,3,4-hexafluorobutane; 1,1,2,2,4,4-hexafluorobutane; 1,1,2,3,3,4-hexafluorobutane; 1,1,2,3,4,4-hexafluorobutane; 1,2,2,3,3,4-hexafluorobutane; 1,1,1,2,2,3,3-heptafluorobutane; 1,1,1,2,2,4,4-heptafluorobutane; 1,1,1,2,2,3,4-heptafluorobutane; 1,1,1,2,3,3,4-heptafluorobutane; 1,1,1,2,3,4,4-heptafluorobutane; 1,1,1,2,4,4,4-heptafluorobutane; 1,1,1,3,3,4,4-heptafluorobutane; 1,1,1,2,2,3,3,4-octafluorobutane; 1,1,1,2,2,3,4,4-octafluorobutane; 1,1,1,2,3,3,4,4-octafluorobutane; 1,1,1,2,2,4,4,4-octafluorobutane; 1,1,1,2,3,4,4,4-octafluorobutane; 1,1,1,2,2,3,3,4,4-nonafluorobutane; 1,1,1,2,2,3,4,4,4-nonafluorobutane; 1-fluoro-2-methylpropane; 1,1-difluoro-2-methylpropane; 1,3-difluoro-2-methylpropane; 1,1,1-trifluoro-2-methylpropane; 1,1,3-trifluoro-2-methylpropane; 1,3-difluoro-2-(fluoromethyl)propane; 1,1,1,3-tetrafluoro-2-methylpropane; 1,1,3,3-tetrafluoro-2-methylpropane; 1,1,3-trifluoro-2-(fluoromethyl)propane; 1,1,1,3,3-pentafluoro-2-methylpropane; 1,1,3,3-tetrafluoro-2-(fluoromethyl)propane; 1,1,1,3-tetrafluoro-2-(fluoromethyl)propane; fluorocyclobutane; 1,1-difluorocyclobutane; 1,2-difluorocyclobutane; 1,3-difluorocyclobutane; 1,1,2-trifluorocyclobutane; 1,1,3-trifluorocyclobutane; 1,2,3-trifluorocyclobutane; 1,1,2,2-tetrafluorocyclobutane; 1,1,3,3-tetrafluorocyclobutane; 1,1,2,2,3-pentafluorocyclobutane; 1,1,2,3,3-pentafluorocyclobutane; 1,1,2,2,3,3-hexafluorocyclobutane; 1,1,2,2,3,4-hexafluorocyclobutane; 1,1,2,3,3,4-hexafluorocyclobutane; and 1,1,2,2,3,3,4-heptafluorocyclobutane.
 40. The process of claim 2 wherein the fluorinated hydrocarbon is selected from the group consisting of difluoromethane, trifluoromethane, 1,1-difluoroethane, 1,1,1-trifluoroethane, fluoromethane, and 1,1,1,2-tetrafluoroethane.
 41. The process of claim 2 wherein the fluorinated hydrocarbon is selected from the group consisting of 1,1,1,3,3,3-hexafluoropropane, 1,1,1,2-tetrafluoroethane, 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-pentafluorobutane, octafluorocyclobutane, and 2,3-dihydrodecafluoropentane.
 42. The process of claim 2 wherein the polymerization medium comprises ethylene.
 43. The process of claim 2 where the polymerization medium comprises propylene.
 44. The process of claim 2 where the fluorinated hydrocarbon is not a perfluorinated C4 to C10 alkane.
 45. The process of claim 2 wherein the polymerization further comprises a hydrocarbon and the fluorinated hydrocarbon is soluble in the hydrocarbon.
 46. The process of claim 2 where the fluorinated hydrocarbon is present at 20 to 90 volume %, based upon the volume of the polymerization medium.
 47. The process of claim 2 wherein the fluorinated hydrocarbon is present at least 1 weight % based upon the weight of the fluorinated hydrocarbon and any hydrocarbon solvent or diluent present, and where the process further comprises recovering a polymer having an Mw of 70,000 or more and a percent crystallinity of 20% or more.
 48. The process of claim 2 further comprising introducing a fluorinated hydrocarbon into the polymer effluent.
 49. The process of claim 38 wherein z is 2 or more.
 50. The process of claim 2 wherein the process is a continuous process.
 51. The process of claim 2 wherein the olefins are aliphatic or alicyclic hydrocarbons.
 52. The process of claim 2 wherein the olefins are linear or branched alpha-olefins.
 53. The process of claim 2 wherein the olefins are C2 to C40 linear or branched alpha-olefins.
 54. The process of claim 2 wherein the olefins are selected from the group consisting of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, and dodecene.
 55. The process of claim 2 wherein the fluorocarbon consists essentially of hydrofluorocarbons.
 56. The process of claim 2 where the polymer produced has a crystallinity of less than 20%. 